Rubber compositions including a functionalized wax

ABSTRACT

Disclosed herein are rubber compositions suitable for use in tire treads comprising (a) at least one conjugated diene polymer or copolymer; (b) at least one filler; (c) a curative package; and (d) at least one of: (i) from 0.2 to 10 phr of at least one halogenated hydrocarbon wax, or (ii) from 0.2 to 10 phr of at least one silicone-containing wax comprising a functionalized polyalkylsiloxane, a functionalized polyalkylsilsesquioxane resin, or combinations thereof. In certain embodiments, the at least one halogenated hydrocarbon wax is a chlorinated hydrocarbon or a fluorinated hydrocarbon wax.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority to and any other benefit of U.S.Provisional Patent Application Ser. No. 61/605,278, filed Mar. 1, 2012,and entitled “RUBBER COMPOSITIONS INCLUDING A FLUORINATED HYDROCARBONWAX OR A SILICONE-CONTAINING WAX,” the entire disclosure of which isincorporated by reference herein.

FIELD OF THE INVENTION

The disclosure relates to rubber compositions that include a fluorinatedhydrocarbon wax, a silicone-containing wax, or a chlorinated hydrocarbonwax, where the rubber composition is generally suitable for use intires.

BACKGROUND

Rubber tires employing tire treads have been used for more than onecentury. In such tires, the tire tread provides the interface betweenthe tire and the road surface and, thus, is important to the tractionperformance of the tire. Particularly useful for certain applicationsare tire treads with excellent wet traction performance. However, due tonumerous complex factors involved, such as the hysteretic bulkdeformation of the tread rubber induced by road surface asperities, therate of water drainage between the tread rubber and the road,lubrication by trapped water or other possible lubricants, and thepossible adhesive interactions between the tread rubber and the road,the quantitative mechanisms attributable to improved wet tractionperformance are not completely understood.

The present disclosure relates to the surprising discovery that the useof fluorinated hydrocarbon waxes, silicone-containing waxes, orchlorinated hydrocarbon waxes to replace all or a portion of aconventional wax in a rubber composition allows for the alteration ofthe hydrophilic/hydrophobic properties of the rubber composition. Thisalteration of the hydrophilic/hydrophobic properties of the rubbercomposition can contribute to enhancing the wet skid resistance of therubber formed from such composition. Moreover, the use of fluorinatedhydrocarbon waxes, silicone-containing waxes, or chlorinated hydrocarbonwaxes as disclosed herein to replace all or a portion of a conventionalwax in a rubber composition does not significantly impact the bulkmechanical properties of the rubber composition as compared those of arubber composition formed with the conventional wax.

SUMMARY OF THE INVENTION

The present disclosure provides rubber compositions suitable for use intires. In certain embodiments, the present disclosure provides rubbercompositions suitable for use in tire treads comprising at least oneconjugated diene polymer or copolymer containing at least one conjugateddiene monomer and optionally at least one vinyl-containing monomer; atleast one filler in an amount of 5 to 200 phr, wherein a majority of thefiller is carbon black, silica or a combination thereof; a curativepackage; and at least one of (i) from 0.2 to 10 phr of at least onehalogenated hydrocarbon wax, or (ii) from 0.2 to 10 phr of at least onesilicone-containing wax comprising a functionalized polyalkylsiloxane, afunctionalized polyalkylsilsesquioxane resin, or combinations thereof.In certain embodiments, the halogenated hydrocarbon wax is a chlorinatedhydrocarbon wax or a fluorinated hydrocarbon wax.

In certain embodiments, the present disclosure provides rubbercompositions suitable for use in a tire tread comprising at least oneconjugated diene polymer or copolymer comprising at least one conjugateddiene monomer and optionally at least one vinyl-containing monomer, atleast one filler, a curative package, and a halogenated hydrocarbon waxwhere the halogen is fluorine and the wax is utilized in an amount offrom 0.2 to 10 phr.

In certain other embodiments, the present disclosure provides rubbercompositions suitable for use in a tire tread comprising at least oneconjugated diene polymer or copolymer comprising at least one conjugateddiene monomer and optionally at least one vinyl-containing monomer; atleast one filler; a curative package; and from 0.2 to 10 phr of at leastone silicone-containing wax comprising a functionalizedpolyalkylsiloxane, a functionalized polyalkylsilsesquioxane, orcombinations thereof.

In certain other embodiments, the present disclosure provides rubbercompositions suitable for use in a tire tread comprising at least oneconjugated diene polymer or copolymer comprising at least one conjugateddiene monomer and optionally at least one vinyl-containing monomer, atleast one filler, a curative package, and a halogenated hydrocarbon waxwhere the halogen is chlorine and the wax is utilized in an amount offrom 0.2 to 10 phr of at least one chlorinated hydrocarbon wax.

In certain other embodiments, it is contemplated to use 0.2 to 10 phr ofat least one fluorinated hydrocarbon wax; 0.2 to 10 phr of at least onesilicone-containing wax; 0.2 to 10 phr of at least one chlorinatedhydrocarbon wax; or combinations thereof in the rubber compositionsdisclosed herein.

Other aspects of the present disclosure will be apparent from thedescription that follows.

DETAILED DESCRIPTION

The present disclosure is directed to rubber compositions suitable foruse in tires. In accordance with certain embodiments, the rubbercompositions disclosed herein are suitable for use in tire treads andcomprise at least one conjugated diene polymer or copolymer comprisingat least one conjugated diene monomer and optionally at least onevinyl-containing monomer; at least one filler in an amount of 5 to 200phr, wherein a majority of the filler is carbon black, silica or acombination thereof; a curative package; and (i) from 0.2 to 10 phr ofat least one halogenated hydrocarbon wax, or (ii) from 0.2 to 10 phr ofat least one silicone-containing wax. In certain embodiments, thehalogenated hydrocarbon wax is a chlorinated hydrocarbon wax or afluorinated hydrocarbon wax.

Generally, tire rubber compositions are prepared from variouscombinations of elastomers such as conjugated diene polymer orcopolymers; fillers; a curative package; and, amongst other conventionaladditives, waxes. The waxes typically used in such rubber compositionsare hydrocarbon waxes, such as microcrystalline wax, paraffin wax, andthe like. These hydrocarbon waxes are referred to herein as“conventional waxes.” The conventional wax helps to protect thevulcanized rubber composition from degradation, specifically degradationdue to oxidation and ozonolysis. The conventional wax will migrate tothe outer surface of the vulcanized rubber composition and form aprotective layer over the rubber. This protective layer, in turn,impedes the oxidation and ozonolysis that can cause degradation anddeterioration of the vulcanized rubber (often accompanied by a“browning” of the rubber) to occur during the lifetime of the tire.

As mentioned above, the conventional waxes used in tire rubbercompositions are hydrocarbon waxes, such as microcrystalline wax,paraffin wax, and the like. Paraffin waxes are generally unbranched C₂₀to C₄₀ alkane waxes. Microcrystalline waxes are hydrocarbon waxes thatgenerally have a higher percentage of isoparaffinic and naphthenicgroups than paraffin waxes and also have a smaller crystalline structureas compared to the paraffin waxes. In general, the amount ofconventional wax used in tire rubber compositions ranges from 0.2 to 10phr (parts per hundred of rubber, by weight). More commonly, the amountof conventional wax used is from 1 to 2 phr.

The rubber compositions disclosed herein replace all or part of theconventional wax used in tire rubber compositions with a fluorinatedhydrocarbon wax, a silicone-containing wax, or a chlorinated hydrocarbonwax. In certain embodiments, the rubber compositions replace all of theconventional wax used in tire rubber compositions with a chlorinatedhydrocarbon wax; in other words, in such embodiments, the rubbercomposition does not contain any conventional wax. In accordance withcertain embodiments, the surfaces of the vulcanized rubbers preparedfrom the rubber compositions disclosed herein exhibit an adjustedrelative hydrophobicity or hydrophilicity as compared to the surfaces ofvulcanized rubbers formed from rubber compositions prepared using thesame composition, but using conventional waxes instead of thefluorinated hydrocarbon, the silicone-containing, or the chlorinatedhydrocarbon wax(es).

The adjustment of the relative hydrophobicity or hydrophilicity of therubber surface can contribute to the enhancement of the wet tractionperformance of a tire tread made with the rubber compositions disclosedherein. As mentioned above, due to numerous complex factors involved,the quantitative mechanisms attributable to improved wet fractionperformance are not completely understood. However, in combination withother of the complex factors involved, the adjusted relativehydrophobicity or hydrophilicity can act to enhance the wet tractionperformance, particularly, the wet skid resistance of a tire tread madefrom the rubber compositions disclosed herein. For example, tire treadshaving surfaces that are hydrophobic will tend to repulse the water atthe tread surface and will likely facilitate the water drainage frombetween the tire tread's surface and the road surface. Conversely, tiretreads that have a hydrophilic surface will tend to attract water andare more likely to form “adhesive” capillary bridges between the tiretread's surface and the road surface. Thus, by adjusting the relativehydrophobicity or relative hydrophilicity as compared to a vulcanizedrubber made from the same composition but with conventional wax insteadof the fluorinated hydrocarbon wax, the silicone-containing wax, or thechlorinated hydrocarbon wax, the rubber compositions disclosed hereincan contribute to the enhancement of the wet skid resistance of the tiretread. Moreover, the use of the fluorinated hydrocarbon wax(es), thesilicone-containing wax(es), or the chlorinated hydrocarbon wax(es) donot significantly affect certain important bulk mechanical properties ofsuch rubber, including but not limited to properties directed to dynamicviscoelasticity and tensile strength.

In certain embodiments, the rubber compositions disclosed herein include0.2 to 10 phr of at least one fluorinated hydrocarbon wax. Suitabletypes of fluorinated hydrocarbon waxes for use in the rubbercompositions disclosed herein include hydrocarbon waxes having aperfluorocarbon segment, e.g., a hydrocarbyl segment in which allhydrogens have been replaced with fluorine atoms along the carbon chain.An example of this type of wax is a block copolymer having aperfluorocarbon block segment and a hydrocarbon block segment. Incertain embodiments of this type of fluorinated wax, the block copolymeris represented by the general formula F₃C—(CF₂)_(m)—(CH₂)_(n)—CH₃, wherem is an integer ranging from 1 to 40, n is an integer ranging from 3 to40, and n+m must be greater than 18. Thus, in one embodiment, thefluorinated hydrocarbon wax used in the rubber compositions disclosedherein is a block copolymer having a perfluorocarbon block segment and ahydrocarbon block segment.

In certain embodiments of rubber compositions disclosed herein, thehydrocarbon segment of the fluorinated wax is a paraffin segment, i.e.,an unbranched alkane chain having from 20 to 40 carbon atoms. Thus, inone embodiment, n in the general formula described above ranges from 20to 40. In accordance with certain embodiments of the rubber compositionsdisclosed herein, the fluorinated hydrocarbon wax is a fluorinatedparaffin wax.

Suitable fluorinated hydrocarbon waxes used in the rubber compositionsdisclosed herein include from 0.2% to 70% by weight fluorine based onthe total weight of the wax. In certain embodiments, the fluorinatedhydrocarbon wax used includes from 0.2 to 12% by weight fluorine, orfrom 1% to 8% by weight fluorine. In certain embodiments, the rubbercompositions disclosed herein comprise from 0.2 to 10 phr, preferablyfrom 0.5 to 5 phr of at least one fluorinated hydrocarbon wax.Accordingly, because suitable fluorinated hydrocarbon waxes that areutilized may contain varying amounts of fluorine, it should beunderstood that the total amount of fluorination added to the rubbercomposition can be varied by adjusting the amount (phr) of fluorinatedwax added to the rubber composition and/or the fluorine content of thefluorinated wax added to the rubber composition. Therefore, the totalamount of fluorination added to the rubber composition may vary from0.0004 phr to 5 phr (parts fluorine per hundred parts rubber). Incertain embodiments, the amount of fluorination added to the rubbercomposition is from 0.004 to 1.2 phr, from 0.004 to 0.6 phr, from 0.04to 1.2 phr, from 0.04 to 0.6 phr, from 0.1 to 1.2 phr, from 0.1 to 0.6phr, from 0.2 to 1.2 phr or from 0.2 to 0.6 phr.

Based upon general mixing processes commonly used for preparation of thetire rubber composition, it is desirable that the fluorinatedhydrocarbon waxes are solid at room temperature, which hereinafter isdefined as temperatures ranging from 20° C. to 25° C. Thus, fluorinatedhydrocarbon waxes are preferably solid at temperatures ranging from 20°C. to 25° C. In certain embodiments, the fluorinated hydrocarbon waxesare solid at temperatures up to 130° C. Although not preferred, thefluorinated waxes can also be liquid or in gel form at room temperature.

In one or more embodiments, the rubber compositions disclosed hereininclude 0.2 to 10 phr of at least one silicone-containing wax. Suitabletypes of silicone-containing waxes include functionalizedpolyalkylsiloxanes, functionalized polyalkylsilsesquioxane resins, andthe like.

The functionalized polyalkylsiloxanes used as the silicone-containingwax in the rubber compositions disclosed herein, include, but are notlimited to functionalized polydimethylsiloxanes represented by followingtwo general formulas:(CH₃)₃SiO[R¹(CH₃)SiO]_(x)[(CH₃)₂SiO]_(y)Si(CH₃)₃  (I)orR¹(CH₃)₂SiO[(CH₃)₂SiO]_(z)Si(CH₃)₂R¹  (II).where x is an integer from 1 to 1000; where y is an integer from 0 to1000; where z is an integer from 1 to 1000; and where R¹ has from 9 to45 carbon atoms, and R¹ is selected from an aliphatic group, an aralkylgroup, or a perfluorocarbyl group. Thus, suitable types offunctionalized polydimethylsiloxanes include, but are not limited to, apolydimethylsiloxane functionalized with at least one aliphatic grouphaving from 9 to 45 carbon atoms, a polydimethylsiloxane functionalizedwith at least one perfluorocarbyl group having from 9 to 45 carbonatoms, a polydimethylsiloxane functionalized with at least one aralkylgroup having from 9 to 45 carbon atoms, and combinations thereof. Incertain embodiments, the functional groups can be pendant groups (i.e.,side chains) as shown in formula I, end groups as shown in formula II,or combinations thereof.

Examples of suitable aliphatic functional polydimethylsiloxanes used asthe silicone-containing wax in the rubber compositions disclosed hereininclude, but are not limited to, alkyl functional polydimethylsiloxanessuch as cetyl polydimethylsiloxanes, stearyl polydimethylsiloxanes,behenyl polydimethylsiloxanes, cerotyl polydimethylsiloxanes, and thelike; alkenyl functional polydimethylsiloxanes; and alkynyl functionalpolydimethylsiloxanes. In each of these waxes, the aliphatic functionalgroup, i.e., the alkyl group, the alkenyl group, or the alkynyl group,has from 9 to 45 carbon atoms.

Examples of suitable perfluorocarbyl functional polydimethylsiloxanesused as the silicone-containing wax in the rubber compositions disclosedherein include, but are not limited to, perfluoroalkyl functionalpolydimethylsiloxanes having from 9 to 45 carbon atoms. In one or moreembodiments, the perfluoroalkyl functional polydimethylsiloxanes used inthe rubber compositions disclosed herein include other functional groupssuch as carboxyl groups. Particular non-limiting examples ofperfluorocarbyl functional polydimethylsiloxanes includeperfluorononylethyl carboxydecyl lauryl dimethicone (e.g., PECOSILFST-412 available from Phoenix Chemical, Inc. of Somerville, N.J.),perfluorononylethyl carboxydecyl lauryl/behenyl dimethicone (e.g.PECOSIL FST-41222 available from Phoenix Chemical, Inc.),perfluorononylethyl carboxydecyl behenyl dimethicone (e.g., PECOSILFST-422 available from Phoenix Chemical, Inc.), and perfluorononylethylcarboxydecyl hexacosyl dimethicone (e.g., PECOSIL FST-426 available fromPhoenix Chemical, Inc.).

Examples of suitable aralkyl functional polydimethylsiloxanes used asthe silicone-containing wax in the rubber compositions disclosed hereininclude, but are not limited to, phenylalkyl functionalpolydimethylsiloxanes having from 9 to 45 carbon atoms. Particularexamples of such phenylalkyl functional polydimethylsiloxanes includephenylisopropyl dimethicone (e.g., PECOSIL ARS-09 available from PhoenixChemical, Inc.) and lauryl phenylisopropyl dimethicone (e.g., PECOSILARS-12 available from Phoenix Chemical, Inc.).

In certain embodiments, the functionalized polyalkylsilsesquioxaneresins used as the silicone-containing wax in the rubber compositionsdisclosed herein are polymers having a polyalkylsilsesquioxane structurethat can be represented by the general formula R²SiO_(3/2), where R² isan alkyl group and has from 1 to 6 carbon atoms. Thus, examples of thefunctionalized polyalkylsilsesquioxane polymers include, but are notlimited to, functionalized polymethylsilsesquioxanes, functionalizedpolyethylsilsesquioxanes, functionalized polypropylsilsesquioxanes,functionalized polybutylsilsesquioxanes, functionalizedpolypentylsilsesquioxanes, and functionalized polyhexylsilsesquioxanes.

In accordance with one or more embodiments, the functionalizedpolyalkylsilsesquioxane resins are based upon thepolyalkylsilsesquioxane polymers disclosed herein (e.g., R²SiO_(3/2))and include at least one functional group represented by the generalformula R³(CH₃)₂SiO_(1/2), where R³ is an alkyl group and has from 9 to45 carbon atoms. In accordance with certain embodiments, preferably, R³is an alkyl group and has from 30 to 45 carbon atoms.

Moreover, in certain embodiments, the aforementionedpolyalkylsilsesquioxane polymer containing the at least oneR³(CH₃)₂SiO_(1/2) functional group further includes at least onefunctional group represented by the general formula R⁴R⁵SiO_(2/2), whereR⁴ is selected from the group consisting of an alkyl group having from 1to 45 carbon atoms, an alkenyl group having from 2 to 45 carbon atoms,an alkynyl group having from 2 to 45 carbon atoms, a hydroxyl group,sulfhydryl groups, ester groups, ether groups, and acid groups; andwhere R⁵ is selected from the group consisting of an alkyl group havingfrom 1 to 45 carbon atoms, an alkenyl group having from 2 to 45 carbonatoms, an alkynyl group having from 2 to 45 carbon atoms, a hydroxylgroup, sulfhydryl groups, ester groups, ether groups, and acid groups.

In accordance with certain embodiments of the rubber compositiondisclosed herein, the rubber compositions comprise from 0.2 to 10 phr,preferably from 0.5 to 5 phr of the at least one silicone-containingwax. In certain embodiments, the silicone-containing wax used in therubber compositions disclosed herein is selected from functionalizedpolyalkylsiloxanes, functionalized polyalkylsilsesquioxanes, andcombinations thereof.

Based upon general mixing processes used for the preparation of the tirerubber composition, it is desirable that the silicone-containing waxesare solid at room temperature. Thus, the silicone-containing waxes arepreferably solid at temperatures ranging from 20° C. to 25° C. Incertain embodiments, the silicone-containing waxes are solid attemperatures up to 130° C. Although not preferred, thesilicone-containing waxes can also be liquid or in gel form at roomtemperature.

In certain embodiments, the rubber compositions disclosed herein include0.2 to 10 phr of at least one chlorinated hydrocarbon wax. Suitabletypes of chlorinated hydrocarbon waxes for use in the rubbercompositions disclosed herein include hydrocarbon waxes havingchlorocarbon segment, e.g., hydrocarbon segments in which some or allhydrogens have been replaced with chlorine atoms along the carbon chain.In certain embodiments, the chlorinated hydrocarbon wax is a chlorinatedparaffin wax. Suitable, but non-limiting, examples of chlorinatedhydrocarbon waxes suitable for use in the rubber compositions disclosedherein include Chlorez® chlorinated waxes (available from Dover ChemicalCorporation, Dover, Ohio) such as Chlorez 700, Chlorez 700-S, Chlorez760, Chlorez 700-DD, Chlorez 700-SS, and Chlorez 700-SSNP; Chloroflo 40(available from Dover Chemical Corporation, Dover, Ohio), Paroilchlorinated oils (available from Dover Chemical Corporation, Dover,Ohio) such as Paroil 150-LV, Paroil 10-NR and Paroil 63-NR). Notably, asused herein, the term chlorinated hydrocarbon wax should be consideredto include compounds that are solids at room temperature (such as theChlorez® series chlorinated waxes, identified above) and compounds thatare oils at room temperature (such as the Paroil series chlorinatedoils, identified above), unless it is clear from the context that onlycompounds that are solid at room temperature are intended.

Suitable chlorinated hydrocarbon waxes used in the rubber compositionsdisclosed herein include from 30-75% by weight chlorine based on thetotal weight of the wax, preferably from 40 to 75% by weight chlorine.In certain embodiments, the rubber compositions disclosed hereincomprise from 0.2 to 10 phr, preferably from 0.5 to 5 phr, or 1 to 5 phrof at least one chlorinated hydrocarbon wax. Accordingly, becausesuitable chlorinated hydrocarbon waxes that are utilized may containvarying amounts of chlorine, it should be understood that the totalamount of chlorination added to the rubber composition can be varied byadjusting the amount (phr) of chlorinated hydrocarbon wax added to therubber composition and/or the chlorine content of the chlorinatedhydrocarbon wax added to the rubber composition. Therefore, the totalamount of chlorination added to the rubber composition may vary from0.005 to 7.5 phr (parts chlorine per hundred parts rubber in the rubbercomposition). In certain embodiments utilizing chlorinated hydrocarbonwax, the amount of chlorination added to the rubber composition is from1 to 4 phr.

Based upon general mixing processes used for the preparation of tirerubber compositions, it is desirable that the chlorinated hydrocarbonwax is a solid at room temperature. Thus, the chlorinated hydrocarbonwaxes are preferably solid at temperatures ranging from 20° C. to 25° C.In certain embodiments, the chlorinated hydrocarbon waxes are solid attemperatures up to 130° C. Although not preferred, the chlorinatedhydrocarbon waxes can also be liquid (oil) or in gel form at roomtemperature.

In certain embodiments, the halogenated hydrocarbon wax is a brominatedhydrocarbon wax and is present in an amount of 0.2 to 10 phr. In otherembodiments, the halogenated hydrocarbon wax is a brominated hydrocarbonwax and is present in an amount of 0.5 to 5 phr. Various types ofbrominated hydrocarbon waxes may be suitable for use in the embodimentsdisclosed herein, including those containing various weight percentagesof bromine such as 20-75% by weight based upon the weight of the wax,alternatively 35-75% by weight based upon the weight of the wax.Suitable, but non-limiting, examples of brominated hydrocarbon waxessuitable for use in the rubber compositions disclosed herein includeDoverguard® brominated waxes (available from Dover Chemical Corporation,Dover, Ohio), such as Doverguard® 8207-A, Doverguard® 8208-A, andDoverguard® 8408. Notably, certain of these waxes include both chlorineand bromine and, accordingly, as noted in other portions of thisdisclosure, it should be considered to be within the scope of thedisclosure to include a combination of chlorinated hydrocarbon wax andbrominated hydrocarbon wax (either as separate waxes or via introductionof one wax containing both chlorine and bromine).

In certain embodiments, the halogenated hydrocarbon wax is a iodated waxand is present in an amount of 0.2 to 10 phr. In other embodiments, thehalogenated hydrocarbon wax is a iodated hydrocarbon wax and is presentin an amount of 0.5 to 5 phr. Various types of iodated hydrocarbon waxesmay be suitable for use in the embodiments disclosed herein, includingthose containing various weight percentages of iodine such as 20-75% byweight based upon the weight of the wax, alternatively 35-75% by weightbased upon the weight of the wax.

In accordance with one embodiment, it is contemplated that the rubbercompositions may include a combination of at least one fluorinatedhydrocarbon wax as disclosed herein, at least one silicone-containingwax as disclosed herein, and at least one chlorinated hydrocarbon wax.Thus, in accordance with this embodiment, the rubber compositionsdisclosed herein comprise at least one conjugated diene polymer orcopolymer containing at least one conjugated diene monomer andoptionally at least one vinyl-containing monomer, at least one filler, acurative package, at least one fluorinated hydrocarbon wax, at least onesilicone-containing wax, and at least one chlorinated hydrocarbon wax.In this embodiment, the at least one fluorinated hydrocarbon wax, the atleast one silicone-containing wax, and the at least one chlorinatedhydrocarbon wax used in the rubber composition are present in a totalcombined amount of from 0.2 to 10 phr, preferably from 0.5 to 5 phr. Insuch embodiments, the at least one fluorinated hydrocarbon wax, the atleast one silicone-containing wax, and the at least one chlorinatedhydrocarbon wax include, but are not limited to, those described inparagraphs 15-30 herein.

In accordance with one embodiment, it is contemplated that the rubbercompositions may include a combination of at least two of: at least onefluorinated hydrocarbon wax as disclosed herein, at least onesilicone-containing wax as disclosed herein, and at least onechlorinated hydrocarbon wax. Thus, in accordance with this embodiment,the rubber compositions disclosed herein comprise at least oneconjugated diene polymer or copolymer; at least one filler; a curativepackage; and at least two of at least one fluorinated hydrocarbon wax,at least one silicone-containing wax, and at least one chlorinatedhydrocarbon wax. In this embodiment, the fluorinated hydrocarbon wax,the silicone-containing wax, and the chlorinated hydrocarbon wax used inthe rubber composition are present in a total combined amount of from0.2 to 10 phr, preferably from 0.5 to 5 phr. In such embodiments, the atleast one fluorinated hydrocarbon wax, the at least onesilicone-containing wax, and the at least one chlorinated hydrocarbonwax include, but are not limited to, those described in paragraphs 15-30herein.

In accordance with certain embodiments, the rubber compositionsdisclosed herein further include a conventional wax in addition to theat least one fluorinated hydrocarbon wax, the at least onesilicone-containing wax, or combinations thereof. In other embodiments,when the rubber composition utilizes at least one chlorinatedhydrocarbon wax, the rubber composition does not contain anyconventional wax. In other words, all of the wax contained within suchrubber composition is chlorinated hydrocarbon. Examples of suitableconventional waxes for use in the rubber compositions disclosed hereininclude hydrocarbon waxes, such as microcrystalline waxes, paraffinwaxes, and the like. In certain embodiments, the conventional waxincludes a microcrystalline wax, a paraffin wax, and combinationsthereof. In accordance with one or more embodiments, the conventionalwax can be added to the rubber composition in an amount up to 10 phr,such that the total amount of all waxes, i.e., the conventional waxalong with the at least one fluorinated hydrocarbon wax, the at leastone silicone-containing wax, or combinations thereof, does not exceed 10phr.

As mentioned above, the rubber compositions disclosed herein include atleast one conjugated diene polymer or copolymer comprising at least oneconjugated diene monomer and optionally at least one vinyl-containingmonomer. Such conjugated diene polymers and conjugated diene copolymerscan be derived, for example, from the polymerization of one or more ofthe following conjugated diene monomer units 1,3-butadiene, isoprene,1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene,2-ethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene,4-methyl-1,3-pentadiene, 2,4-hexadiene, and combinations thereof.

In certain embodiments, suitable conjugated diene polymers andconjugated diene copolymers used in the tire rubber compositionsdisclosed herein can be derived from the polymerization of one or moreof the conjugated diene monomers disclosed above and one or more vinylaromatic hydrocarbon monomers. Examples of suitable vinyl aromatichydrocarbon monomers include, but are not limited to styrene,α-methylstyrene, p-methylstyrene, o-methylstyrene, p-butylstyrene,vinylnaphthalene, and combinations thereof.

Examples of suitable conjugated diene polymers and conjugated dienecopolymers for use in the rubber compositions disclosed herein include,but are not limited to, polyisoprene, polybutadiene, butadiene-isoprenecopolymer, butadiene-isoprene-styrene copolymer, isoprene-styrenecopolymer, styrene-butadiene copolymer, natural rubber, butyl rubber,halogenated butyl rubber, and combinations thereof. In accordance withthe rubber compositions disclosed herein, the rubber compositionscomprise a combined amount of 100 phr of the at least one conjugateddiene polymer or copolymer.

In certain embodiments, the conjugated diene polymer or copolymer (asdescribed above) within the rubber composition is functionalized with afunctional chemical group at one end, both ends, or along the backboneof the polymer or copolymer. In certain embodiments, the conjugateddiene polymer or copolymer is functionalized or coupled with a tin orsilica-containing compound such as with tin tetrachloride, dibutyl tinchloride, or with another suitable compound, non-limiting examples ofwhich include cyclic amines, polyisocanates, cyclic ureas, a silylchloride, polyisocyanates, carbodiimides, polyepoxides, andalkoxysilanes.

The rubber compositions disclosed herein include at least one filler.Generally, any filler(s) conventionally used to prepare rubbercompositions can be used in the rubber compositions described herein.Examples of suitable fillers used in the rubber compositions disclosedherein include, but are not limited to, reinforcing fillers such ascarbon black; silica; mineral fillers such as clay (e.g., hydrousaluminum silicate), exfoliated clay, talc (hydrous magnesium silicate),aluminum hydrate (Al(OH)₃), and mica; as well as metal oxides such asaluminum oxide; titanium dioxide, and the like. Additional usefulfillers suitable for use in the rubber compositions disclosed herein areknown to those skilled in the art.

As previously discussed, in certain embodiments, the amount of the atleast one filler that is contained within the rubber composition is5-200 phr, wherein a majority of the filler is carbon black, silica or acombination thereof. In certain such embodiments, the 5-200 phr of atleast one filler is selected from the group consisting of carbon black,silica, clay, metal oxides, and combinations thereof, keeping in mindthat a majority of the filler is carbon black, silica or a combinationthereof. In certain embodiments, the amount of the at least one fillerthat is contained within the rubber composition is 5-100 phr, and amajority of the filler is carbon black, silica or a combination thereof.In such embodiments the 5-100 phr of at least one filler is selectedfrom the group consisting of carbon black, silica, clay, metal oxides,and combinations thereof. In certain embodiments where the rubbercomposition contains 0.5-10 phr (or alternatively 0.5 to 5 phr) of atleast one chlorinated hydrocarbon wax, the rubber composition contains5-100 phr of at least one filler; in certain such embodiments, the 5-100phr of at least one filler is selected from the group consisting ofsilica, clay, metal oxides, and combinations thereof (i.e., the at leastone filler excludes carbon black), wherein a majority of the filler iscarbon black, silica or a combination thereof.

Examples of suitable types of carbon blacks used as the filler incertain embodiments of the tire rubber composition disclosed hereininclude furnace blacks, channel blacks, and lamp blacks. Morespecifically, examples of suitable carbon blacks include super abrasionfurnace (SAF) blacks, high abrasion furnace (HAF) blacks, fast extrusionfurnace (FEF) blacks, fine furnace (FF) blacks, intermediate superabrasion furnace (ISAF) blacks, semi-reinforcing furnace (SRF) blacks,medium processing channel blacks, hard processing channel blacks, andconducting channel blacks. Other examples of suitable carbon blacksinclude, but are not limited to, acetylene blacks. Furthermore, amixture of two or more of the aforementioned carbon blacks can be usedas the filler in certain embodiments of the tire rubber compositiondisclosed herein. The grades of the carbon blacks suitable for use incertain embodiments of the rubber compositions disclosed herein arethose characterized by ASTM D-1765, such as N-110, N-134, N-220, N-339,N-330, N-351, N-550, N-660, and N990 grades. Other grades of carbonblack may also be suitable for use in certain embodiments of the rubbercompositions disclosed herein, either alone, in combination or incombination with the previously listed grades of carbon black.

The carbon blacks used in accordance with embodiments of the tire rubbercomposition disclosed herein can be in a pelletized form or anunpelletized flocculent mass. For more uniform mixing, unpelletizedcarbon black is preferred.

Examples of silica used as the filler in certain embodiments of the tirerubber composition disclosed herein include, but are not limited to,precipitated amorphous silicas, dry silicas such as fumed silica,calcium silicate, and the like. Other suitable fillers include aluminumsilicate, magnesium silicate, and the like.

In certain embodiments of the tire rubber composition disclosed herein,a silane coupling agent is used when silica or some other type ofinorganic particles are used as the filler. In such embodiments, thesilane coupling agent helps bond the filler to the conjugated dienepolymer or copolymer (i.e., the elastomer), thereby improving the wearresistance of the vulcanized rubber composition. Examples of suitablesilane coupling agents include, but are not limited to, functionalizedpolysulfide silanes such as bis(trialkoxysilylorgano) polysulfidesilanes and thiocarboxylate functional silanes such as a3-octanoylthio-1-propyltriethoxysilane. Commercial examples of thefunctionalized polysulfide silane coupling agents are sold under theregistered trademarks SI 75 and SI 69 (both are available from EvonikIndustries of Germany). A commercial example of a thiocarboxylatefunctional silane is sold under the registered trademark NXT (availablefrom Momentive Performance Materials of Wilton, Conn.).

In accordance with certain embodiments, the fillers used in the rubbercompositions disclosed herein include at least one of carbon black,silica, clay, metal oxides, or combinations thereof. Preferably, therubber compositions disclosed herein include at least one of carbonblack, silica, or combinations thereof. In accordance with certainembodiments, the rubber composition comprises a combined amount of 5 to200 phr of at least one filler, preferably 30 to 100 phr, wherein amajority of the filler is carbon black, silica or a combination thereof.One skilled in the art will understand that the amount of filler that isused in the rubber compositions disclosed herein may depend on certainproperties of the filler such as its specific surface area, itsstructure, its interaction with polymer(s), and its specific gravity.Accordingly, those skilled in the art will be able to select a suitableamount of the filler(s) based on the properties of the filler(s).

As mentioned above, the rubber compositions disclosed herein include acurative package. In accordance one or more embodiments, a curativepackage includes at least one vulcanizing agent and optionally any of:vulcanizing accelerators; vulcanizing activators such as zinc oxide,stearic acid, and the like; vulcanizing inhibitors; anti-scorch agents;and the like. A “vulcanizing agent” refers to the compounds used alone,or as part of a system, to cure, i.e., crosslink, the rubber compositionduring vulcanization. In certain embodiments, the curative packageincludes at least one vulcanizing agent and at least one vulcanizingaccelerator. In other embodiments, the curative package includes atleast one vulcanizing agent, at least one vulcanizing accelerator, andat least one vulcanizing activator. In yet other embodiments, thecurative package includes at least one vulcanizing agent, at least onevulcanizing accelerator, at least one vulcanizing activator, and atleast one vulcanizing inhibitor. In still other embodiments, thecurative package includes at least one vulcanizing agent, at least onevulcanizing accelerator, at least one vulcanizing activator, at leastone vulcanizing inhibitor, and at least one anti-scorching agent.

Examples of suitable types of vulcanizing agents used in the rubbercompositions disclosed herein, include but are not limited to, sulfur orperoxide-based curing systems. Examples of specific suitable sulfurvulcanizing agents used in the rubber compositions disclosed hereininclude “rubbermaker's” soluble sulfur; sulfur donating curing agents,such as an amine disulfide, polymeric polysulfide or sulfur olefinadducts; and insoluble polymeric sulfur. Preferably, the sulfurvulcanizing agent is soluble sulfur or a mixture of soluble andinsoluble polymeric sulfur. For a general disclosure of suitablevulcanizing agents, one can refer to Kirk-Othmer, Encyclopedia ofChemical Technology, 3rd ed., Wiley Interscience, N.Y. 1982, Vol. 20,pp. 365 to 468, particularly Vulcanization Agents and AuxiliaryMaterials, pp. 390 to 402, or Vulcanization by A. Y. Coran, Encyclopediaof Polymer Science and Engineering, Second Edition (1989 John Wiley &Sons, Inc.), both of which are incorporated herein by reference.Vulcanizing agents can be used alone or in combination. The sulfurvulcanizing agents are used in an amount ranging from 0.1 to 10 phr, 0.2to 7.5 phr, and preferably from 0.2 to 5 phr.

Vulcanizing accelerators are used to control the time and/or temperaturerequired for vulcanization and to improve properties of the vulcanizate.Examples of suitable vulcanizing accelerators used in the rubbercompositions disclosed herein include, but are not limited to, thiazolevulcanization accelerators, such as 2-mercaptobenzothiazole,2,2′-dithiobis(benzothiazole) (MBTS),N-cyclohexyl-2-benzothiazole-sulfenamide (CBS),N-tert-butyl-2-benzothiazole-sulfenamide (TBBS), and the like; guanidinevulcanization accelerators, such as diphenyl guanidine (DPG) and thelike; thiuram vulcanizing accelerators; carbamate vulcanizingaccelerators; and the like. The amount of the vulcanization acceleratorused ranges from 0.1 to 7 phr, preferably 0.2 to 5 phr.

In certain embodiments, process oils can be used to extend and softenthe rubber compositions disclosed herein. Examples of suitable processoils that may be used include, but are not limited to, paraffinic oils,aromatic oils, naphthenic oils, vegetable oils other than castor oils,and low polycyclic aromatic content (“low PCA oils”). Low PCA oils areoils that contain less than 3 wt % polycyclic aromatic content (asmeasured by IP346). Examples of such low PCA oils useful for the rubbercompositions disclosed herein include various naphthenic oils, mildextraction solvates (MES) and treated distillate aromatic extracts(TDAE). In certain embodiments, the process oil comprises Black Oil. Upto 100 phr of process oil can be used with certain embodiments of thetire rubber composition disclosed herein; in other embodiments, between0 and 50 phr; in yet other embodiments between 0 and 20 phr.

Other additives that can be used in the rubber compositions disclosedherein are also well known to those of skill in the art and includeresins, such as tackifying resins, reinforcing resins, and the like;plasticizers; pigments; additional fillers; fatty acids such as stearicacid; zinc oxide; antioxidants such as diphenyl-p-phenylenediamine(DPPD), N-(1,3-dimethylbutyl)-N″-phenyl-1,4-benzenediamine (6PPD), andthe like; anti-ozonants; peptizing agents; and one or more additionalrubbers.

The rubber compositions disclosed herein are useful for differentcomponents of a pneumatic tire, including but not limited to, treads,subtreads, black sidewalls, bead fillers, and the like. In accordancewith a preferred embodiment, the rubber compositions disclosed hereinare used as a tire tread.

The rubber compositions disclosed herein can be prepared using standardequipment such as, e.g., Banbury or Brabender mixers. For furtherexplanation of rubber compounding and the additives conventionallyemployed, one can refer to The Compounding and Vulcanization of Rubber,by Stevens in Rubber Technology, Second Edition (1973 Van NostrandReibold Company), which is incorporated herein by reference. Typically,the rubber compositions disclosed herein are prepared using two or moremixing stages. During the first stage (also known as the “master batch”stage), ingredients including the rubber components and fillers aremixed. The mixing during this stage typically occurs at temperatures ofabout 100° C. to about 200° C. for a period of time or until a dischargeor drop temperature, typically about 165° C., is reached. To preventpremature vulcanization (also known as scorch), this initial masterbatchmay exclude any vulcanizing agents or other components of the curativepackage.

For certain rubber compositions such as where a formulation includeshigher amounts of filler or fillers other than (or in addition to)carbon black, a separate re-mill stage may be employed for separateaddition of the other fillers in order to reduce the compound viscosityand improve the dispersion of the fillers. This stage often is performedat temperatures similar to, although often slightly lower than, thoseemployed in the master batch stage.

Most or all of the components of the curative package, e.g., vulcanizingagents, vulcanizing accelerators, vulcanizing activators, etc., aregenerally added at a final mixing stage. To avoid undesirable scorchingand/or premature onset of vulcanization, this mixing step often is doneat lower temperatures, e.g., starting at about 60° C. to about 75° C.and not going higher than about 105° C. to about 110° C. As referred toherein, the term “final batch” means the composition that is presentduring the final mixing stage. Typically, when the rubber compositionsare to be used in tires, vulcanization is effected by heating thevulcanizable composition in a mold under pressure. Pneumatic tires canbe made as disclosed in U.S. Pat. Nos. 5,866,171, 5,876,527, 5,931,211,and 5,971,046, which are incorporated herein by reference.

Depending upon the ultimate use for the rubber composition, it may beprocessed (e.g., milled) into sheets prior to being formed into any of avariety of components and then vulcanized, which typically occurs atabout 5° C. to about 15° C. higher than the highest temperaturesemployed during the mixing stages, most commonly about 170° C.

In accordance with one embodiment of the tire rubber compositionsdisclosed herein, the rubber composition comprises (a) at least oneconjugated diene polymer or copolymer containing at least one conjugateddiene monomer and optionally at least one vinyl-containing monomer; (b)at least one filler in an amount of 5 to 200 phr, wherein a majority ofthe filler is carbon black, silica, or a combination thereof; (c) acurative package; and (d) at least one of: (i) from 0.2 to 10 phr of atleast one halogenated hydrocarbon wax, or (ii) from 0.2 to 10 phr of atleast one silicone-containing wax comprising a functionalizedpolyalkylsiloxane, a functionalized polyalkylsilsesquioxane resin, orcombinations thereof. In certain embodiments, the halogenatedhydrocarbon wax is a chlorinated hydrocarbon wax or a fluorinatedhydrocarbon wax. In certain embodiments, the rubber compositioncomprises from 0.5 to 5 phr of the at least one fluorinated hydrocarbonwax. In other embodiments, the rubber composition comprises from 0.5 to5 phr of the at least one silicone-containing wax. In yet otherembodiments, the rubber compositions comprises from 0.5 to 5 phr of theat least one chlorinated hydrocarbon wax.

In certain of the preceding embodiments, the at least one fluorinatedhydrocarbon wax comprises 0.2% to 70% by weight fluorine based on thetotal weight of the wax. In other embodiments, the at least onefluorinated hydrocarbon wax comprises 0.2 to 12% by weight fluorinebased on the total weight of the wax. Moreover, in certain of thepreceding embodiments, the at least one fluorinated hydrocarbon waxcomprises a fluorinated paraffin wax. In addition, in accordance withcertain of the preceding embodiments, the at least one fluorinatedhydrocarbon wax is solid at temperatures from 20° C. to 25° C.

In certain of the preceding embodiments, the at least one chlorinatedhydrocarbon wax comprises 35-75% by weight chlorine based on the totalweight of the wax. Moreover, in certain of the preceding embodiments,the at least one chlorinated hydrocarbon wax comprises a chlorinatedparaffin wax. In addition, in accordance with certain of the precedingembodiments, the at least one chlorinated hydrocarbon wax is solid attemperatures from 20° C. to 25° C.

As mentioned above, in certain of the preceding embodiments, the atleast one silicone-containing wax comprises a functionalizedpolyalkylsiloxane. In accordance with certain of the precedingembodiments, the functionalized polyalkylsiloxane is a functionalizedpolydimethylsiloxane. In addition, in accordance with certain of thepreceding embodiments, the functionalized polyalkylsiloxane is selectedfrom the group consisting of an alkyl functional polydimethylsiloxane,an alkenyl functional polydimethylsiloxane, an alkynyl functionalpolydimethylsiloxane, a perfluoroalkyl functional polydimethylsiloxane,and combinations thereof. In certain of the preceding embodiments, thealkyl functional group of the alkyl functional polydimethylsiloxane hasfrom 9 to 45 carbon atoms.

As mentioned above, in certain of the preceding embodiments, thesilicone-containing wax comprises a functionalizedpolyalkylsilsesquioxane resin. In accordance with certain embodiments,the functionalized polyalkylsilsesquioxane resin includes at least onefunctional group represented by the general formula R³(CH₃)₂SiO_(1/2),where R³ is an alkyl group and has from 30 to 45 carbon atoms. Furtherin accordance with the preceding embodiment, the functionalizedpolyalkylsilsesquioxane resin further includes at least one functionalgroup represented by the general formula R⁴R⁵SiO_(2/2), where R⁴ isselected from the group consisting of an alkyl group having from 1 to 45carbon atoms, an alkenyl group having from 2 to 45 carbon atoms, analkynyl group having from 2 to 45 carbon atoms, a hydroxyl group,sulfhydryl groups, ester groups, ether groups, and acid groups; andwhere R⁵ is selected from the group consisting of an alkyl group havingfrom 1 to 45 carbon atoms, an alkenyl group having from 2 to 45 carbonatoms, an alkynyl group having from 2 to 45 carbon atoms, a hydroxylgroup, sulfhydryl groups, ester groups, ether groups, and acid groups.

As mentioned above, certain embodiments of the rubber compositionsdisclosed herein comprise (a) at least one conjugated diene polymer orcopolymer; (b) at least one filler; (c) a curative package; (d) at leastone of: (i) from 0.2 to 10 phr of at least one halogenated hydrocarbonwax, or (ii) from 0.2 to 10 phr of at least one silicone-containing waxcomprising a functionalized polyalkylsiloxane, a functionalizedpolyalkylsilsesquioxane resin, or combinations thereof. In certainembodiments, the halogenated hydrocarbon wax is a chlorinatedhydrocarbon wax or a fluorinated hydrocarbon wax. In certainembodiments, the rubber composition further comprises a conventional waxselected from the group consisting of a microcrystalline wax, a paraffinwax, and combinations thereof.

As also mentioned above, the rubber compositions disclosed hereininclude at least one conjugated diene polymer or copolymer. Inaccordance with certain embodiments of the rubber compositions disclosedherein, the at least one conjugated diene polymer or copolymer isderived from monomer units selected from the group consisting of1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene,2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene,2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene,4-methyl-1,3-pentadiene, 2,4-hexadiene, styrene, α-methylstyrene,p-methylstyrene, o-methylstyrene, p-butylstyrene, vinylnaphthalene, andcombinations thereof.

As mentioned above, the rubber compositions disclosed herein include atleast one filler. In accordance with certain embodiments of the rubbercompositions disclosed herein, the at least one filler is selected fromthe group consisting of carbon black, silica, clay, metal oxides, andcombinations thereof.

Moreover, in certain of the preceding embodiments, the at least oneconjugated diene polymer or copolymer is present in an amount of 100 phrand is selected from the group consisting of polybutadiene, astyrene-butadiene copolymer, polyisoprene, natural rubber, andcombinations thereof; and the at least one filler is present in anamount of from 5 to 100 phr and is selected from the group consisting ofcarbon black, silica, clay, metal oxides, and combinations thereof.

Rubber compositions according to the embodiments disclosed hereinexhibit an adjusted surface hydrophobicity or hydrophilicity as measuredby a contact angle with water different from that of a rubber formedfrom a comparative composition. The comparative composition refers toone with the same rubber composition except containing a conventionalwax instead of either (i) from 0.2 to 10 phr of at least one halogenatedhydrocarbon wax, or (ii) from 0.2 to 10 phr of at least onesilicone-containing wax, and the conventional wax is present in the sameamount as either (i), or (ii).

In another embodiment, the present disclosure provides a tire containinga tread comprising the rubber compositions disclosed herein.

EXAMPLES

The following examples are for purposes of illustration only and are notintended to limit the scope of the claims which are appended hereto.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which the technology of this application belongs. While thepresent application has been illustrated by the description ofembodiments thereof, and while the embodiments have been described inconsiderable detail, it is not the intention of the applicants torestrict or in any way limit the scope of the appended claims to suchdetail. Additional advantages and modifications will readily appear tothose skilled in the art. Therefore, the application, in its broaderaspects, is not limited to the specific details, the representativeembodiments, and illustrative examples shown and described. Accordingly,departures may be made from such details without departing from thespirit or scope of the applicant's general inventive concept.

Examples 1-6

Six rubber compositions were prepared within a Brabender internal mixer(65 gram capacity) according to the formulations shown Table 1, usingvarying agitation speeds as shown in Table 1A below. As detailed inTables 1 and 1A, a two stage mixing procedure was employed. (Unlessindicated otherwise, all amounts of ingredients in the Tables are listedin terms of phr, parts per hundred parts rubber.)

TABLE 1 Formulation (phr) Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 MasterBatch Styrene butadiene^(a) 100 100 100 100 100 100 Carbon black^(b) 5050 50 50 50 50 Black oil 10 10 10 10 10 10 Stearic acid 2.0 2.0 2.0 2.02.0 2.0 6PPD^(c) 0.95 0.95 0.95 0.95 0.95 0.95 Conventional wax^(d) 2.00 0 0 0 0 Hydrocarbon wax^(e) 0 2.0 0 0 0 0 Lightly fluorinated wax^(f)0 0 2.0 0 0 0 Highly fluorinated wax 0 0 0 2.0 0 0 1^(g) Highlyfluorinated wax 0 0 0 0 2.0 0 2^(h) Silicone wax^(i) 0 0 0 0 0 2.0 FinalBatch Zinc oxide 2.5 2.5 2.5 2.5 2.5 2.5 DPG^(j) 0.3 0.3 0.3 0.3 0.3 0.3MBTS^(k) 0.5 0.5 0.5 0.5 0.5 0.5 TBBS^(l) 0.5 0.5 0.5 0.5 0.5 0.5 Sulfur1.5 1.5 1.5 1.5 1.5 1.5 ^(a)DURADENE 706 available from FirestonePolymers of Akron, OH. ^(b)N343 carbon black. ^(c)Antioxidant 6PPD.^(d)Microcrystalline wax blend: 20% microcrystalline and 80% paraffin;melting point ~170° F. (available from Crystal, Inc., United States)^(e)100 wt % Paraffin ski wax (SWIX CH8 wax available from Swix Sport ASof Norway). ^(f)Fluorinated hydrocarbon ski wax having 0.616 wt %fluorine based on the total weight of the wax (SWIX LF8 wax availablefrom Swix Sport AS). ^(g)Fluorinated hydrocarbon ski wax having 4.69 wt% fluorine based on the total weight of the wax (SWIX HF8 wax availablefrom Swix Sport AS). ^(h)Fluroinated hydrocarbon ski wax having 5.82 wt% fluorine based on the total weight of the wax (SWIX HF8BW waxavailable from Swix Sport AS). ^(i)Polydimethylsiloxane having aliphaticgroups (WACKER W23 Silicone Wax available from Wacker Chemie AG ofGermany) ^(j)Diphenyl guanidine. ^(k)2,2′-Dithiobis(benzothiazole).^(l)N-tert-butyl-2-benzothiazole-sulfenamide.

TABLE 1A Stage Time Condition Master Batch Stage (initial 0 min Chargepolymers temp: 130-135° C., rotor 0.5 min Charge oil, filler and rpmstarted at 60 and other master batch increased to 90 at 4.5 min)ingredients 5.5 min Drop based on time or max temperature of 165° C.Final Batch Stage (initial 0 sec Charge master batch temp: 60-65° C.,rotor rpm 30 seconds Charge curatives at 40) 150 seconds Drop on mixingtime or max temperature of 110° C.

As shown in Table 1, Examples 1 and 2 were prepared as controls usinghydrocarbon-only waxes instead of the fluorinated hydrocarbon orsilicone-containing waxes used in Examples 3-6.

The bound rubber percentage for each Examples 1-6 was determined bysolvent extraction with toluene at room temperature. More specifically,multiple small specimens of each uncured rubber sample (total weightabout 0.2 g) were placed into a cylinder with 40 mesh stainless steelscreen at the bottom and immersed in toluene for three days. The solventwas removed and the remaining specimens on the screen were dried andweighed. The percentage of bound rubber was then determined according tothe formula percent (by weight) bound rubber=(100(W_(d)−F))/R whereW_(d) is the weight of the remains of the dried specimens, F is theweight of the filler and any other solvent insoluble matter in theoriginal sample, and R is the weight of the rubber in the originalsample. The bound rubber percentages measured for Examples 1-6 are shownin Table 2 below.

Following the final batch stage, the rubber compositions were sheetedinto specimens of different shapes for each of Examples 1-6, which inturn were respectively used in the different tests described inparagraphs 66-69 below. The specimens were then cured at 165° C. for aproper duration as determined by a cure test for the composition fromeach Example, thereby forming respective differently shaped vulcanizatespecimens for each of Examples 1-6. The vulcanizate specimens forExamples 1-6 were subject to various tests, and the results of thosetests are provided in Table 2 below.

The dynamic viscoelastic properties of the vulcanizate specimens weremeasured by three different tests. The first dynamic viscoelastic testwas a temperature sweep test performed using an ARES (AdvancedRheometric Expansion System) from TA Instruments. The test specimen hada rectangular geometry having a thickness of 2 mm, and a width of 12.7mm. The length of specimen between the grips on the test machine, i.e.,the gap, was approximately 28 mm. The test was conducted using afrequency of 10 Hz. The temperature was started at −70° C. and increasedto 120° C. The strain was 0.20% for the temperature range of −70° C. to−6° C., and 2.0% for the temperature range of −5° C. to 120° C.

The second dynamic viscoelastic test was a dynamic strain sweep testperformed using an ARES from TA Instruments. The test was carried out ina parallel plate geometry with a rubber button test specimen having adiameter of 7.8 mm and a height of 6 mm. The test was conducted using afrequency of 15 Hz. The temperature was held constant at the desiredtemperature, which was 50° C. The strain was swept from 0.1% to 24.6%,logarithmically.

The third viscoelastic test was a dynamic compression test performedusing a DYNASTAT mechanical spectrometer from Dynastatics InstrumentsCorp. The test was carried out using a cylindrical test specimen havinga 9.3 mm diameter and a 15 mm height. The sample was compressed under astatic load of 2 kg before testing. After it reached an equilibriumstate, the test started with a dynamic load having an amplitude of 1.25kg at a frequency of 10 Hz and at a temperature of 60° C. The sample wasthus cyclically deformed. The resulting hysteresis (tangent δ)measurements from this test are shown in Table 2 below.

Tensile mechanical properties of the vulcanizate samples were determinedfollowing the guidelines, but not restricted to, the standard proceduredescribed in ASTM D-412, using dumbbell-shaped samples with across-section dimension of 4 mm in width and 1.9 mm in thickness at thecenter. Specimens were strained at a constant rate and the resultingforce was recorded as a function of extension (strain). Force readingsare shown in Table 2 below as engineering-stresses by reference to theoriginal cross-sectional area of the test piece. The specimens weretested at 23° C.

TABLE 2 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 bound rubber % (weight) 24.425.2 24.6 24.8 24.4 24.0 Temp. Sweep at 10 Hz peak tan δ 0.743 0.7290.736 0.738 0.745 0.767 T at peak tan δ (° C.) −46.1 −46.1 −46.0 −46.1−45.9 −46.1 Strain Sweep at 50° C. & 15 Hz G′ at 9.8% (MPa) 2.44 2.482.51 2.49 2.64 2.62 tan δ at 9.8% 0.195 0.197 0.192 0.197 0.190 0.194Dynastat at 60° C. & 10 Hz tan δ 0.176 0.179 0.174 0.179 0.175 0.174Tensile at RT Mod50% (MPa) 1.78 1.75 1.75 1.74 1.79 1.87 Mod300% (MPa)14.96 13.89 14.91 14.14 14.95 15.66 Tb^(a) (MPa) 21.9 20.4 20.2 21.119.4 22.7 Eb^(b) % 421.0 428.6 393.0 429.0 378.9 420.1 ^(a)Tension atbreak ^(b)Elongation at break

As shown in Table 2, the use of the fluorinated hydrocarbon waxes(Examples 3-5) and the silicone-containing wax (Example 6) does notsignificantly impact the bound rubber percent or the bulk mechanicalproperties, i.e., dynamic viscoelastic properties and tensile mechanicalproperties, as compared to the control Examples 1 and 2 (using thehydrocarbon waxes). However, Table 3 below, shows that the respectiveuse of the fluorinated hydrocarbon waxes and the silicone-containing waxin Examples 3-6 does affect the relative hydrophobicity orhydrophilicity of vulcanizate samples.

A Ramé-Hart Model 500 Advanced Goniometer was used to measure thecontact angle of deionized water located on the surface of thevulcanizate samples. The measured contact angle is indicative of therelative hydrophobicity and hydrophilicity of the vulcanizate samplesurface. In general, a surface where the measured contact angle ofdeionized water is greater than 90° is a relatively hydrophobic surface.A surface where the measured contact angle of deionized water is lessthan 90° is relatively hydrophilic. Accordingly, as the contact angleincreases for water, the surface becomes relatively more hydrophobic.

For the contact angle measurement, a specimen was cut from a flatvulcanizate sheet of each Example. Each specimen was 1.9 mm thick forthis measurement. The measurements were made by placing a 3.6-4.0 μLdrop of deionized water either (A) on the surface 72 hours after thesurface was first wiped with acetone and then dried in a vacuum ovenheated to 45° C. for 10 minutes, or (B) directly on the surface withoutany cleaning. From three to eight drops were measured at differentlocations on each specimen's surface. The results of these measurementsare provided in Table 3 below. The values in Table 3 are listed as theaverage measurement±the standard deviation.

TABLE 3 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Contact Clean 100.4 ± 1.0104.2 ± 0.8 102.6 ± 2.0 119.4 ± 4.6 121.5 ± 1.1 105.9 ± 1.9 angleSurface (°) (A) Surface 104.0 ± 0.8 109.6 ± 1.5 109.7 ± 2.9 126.1 ± 8.7130.6 ± 5.9  97.2 ± 4.5 without Cleaning (B)

The results provided in Table 3 show that the use of fluorinatedhydrocarbon waxes (Examples 3-5) or a silicone-containing wax (Example6) adjusts the relative hydrophobicity or hydrophilicity of thevulcanizate as compared to the control vulcanizates of Examples 1 and 2prepared using a hydrocarbon-only wax. Table 3 also shows that therelative hydrophobicity of the samples prepared with the fluorinatedhydrocarbon waxes increases as the percent of the fluorine in the wax,as measured by weight, increases. Specifically, the contact angleincreases between Examples 3 and 4 as well as between Examples 4 and 5.Each of Examples 3, 4, and 5 are prepared using fluorinated hydrocarbonwaxes having different fluorine contents. As shown in Table 1 above,these Examples 3-5 are prepared using the same amount of wax (2 phr).However, the wax used in Example 3 is a fluorinated hydrocarbon ski waxhaving 0.616 wt % fluorine based on the total weight of the wax (SWIXLF8). The wax used in Example 4 is a fluorinated hydrocarbon ski waxhaving 4.69 wt % fluorine based on the total weight of the wax (SWIXHF8). The wax used in Example 5 is a fluorinated hydrocarbon ski waxhaving 5.82 wt % fluorine based on the total weight of the wax (SWIXHF8BW). Thus, as the content of the fluorine increases in eachfluorinated hydrocarbon wax (as measured by weight percent), therelative hydrophobicity also increases as measured by the contact angleof water in these Examples.

All of the Examples containing fluorinated hydrocarbon wax (i.e.,Examples 3-5) had an increase in hydrophobicity as compared to controlExample 1 (containing conventional paraffin wax). Examples 4 and 5(containing relatively higher amounts of fluorine) also showed anincrease in hydrophobicity as compared to control Example 2 (containingconventional hydrocarbon wax). Interestingly, the Example containing thesilicone wax (Example 6), became less hydrophobic without first cleaningthe surface as compared to both control Examples and the clean surfaceversion of this Example.

Examples 7-15

Nine additional rubber compositions were prepared according to theformulations shown in Table 4 in a manner similar to those preparedabove using varying agitation speeds as shown in Table 4A below, exceptthat a 300-gram capacity mixer was utilized and a three-stage mixingprocedure (employing a remill as a second step in the master batchstage) instead of a two-stage mixing procedure was used. The three stagemixing procedure employed is detailed in Table 4A below.

TABLE 4 Formulation Ex. Ex. Ex. Ex. Ex. Ex. (phr) Ex. 7 Ex. 8 Ex. 9 1011 12 13 14 15 Master Styrene 100 100 100 100 100 100 100 100 100 batchbutadiene Silica^(b) 52.5 52.5 52.5 52.5 52.5 52.5 52.5 52.5 52.5 Blackoil 10 10 10 10 10 10 10 10 10 Stearic acid 2 2 2 2 2 2 2 2 2 6PPD^(c) 11 1 1 1 1 1 1 1 Conventional 2 0 0 0 0 0 0 0 0 wax^(d) Silicone wax1^(e) 0 2 5 0 0 0 0 0 0 Silicone wax 2^(f) 0 0 0 2 5 0 0 0 0 Fluorinated0 0 0 0 0 2 5 0 0 silicone wax 1^(g) Fluorinated 0 0 0 0 0 0 0 2 5silicone wax 2^(h) Remill Silica^(b) 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5Silane^(i) 5 5 5 5 5 5 5 5 5 Final Zinc oxide 2.5 2.5 2.5 2.5 2.5 2.52.5 2.5 2.5 batch DPG^(j) 1.4 1.4 1.4 1.4 1.4 1.4 1.4 1.4 1.4 MBTS^(k) 22 2 2 2 2 2 2 2 TBBS^(m) 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 Sulfur 1.51.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 ^(a)DURADENE 706 (available fromFirestone Polymers of Akron, Ohio). ^(b)HI-SIL 190 available from PPG ofPittsburgh, Pennsylvania. ^(c)Antioxidant 6PPD. ^(d)Microcrystalline waxblend: 20% microcrystalline and 80% paraffin; melting point ~170° F.(available from Crystal, Inc., United States). ^(e)Behenylpolydimethylsiloxane (PECOSIL AS-22). ^(f)Cerotyl polydimethylsiloxane(PECOSIL AS-26). ^(g)Perfluorononylethyl carboxydecyl behenylpolydimethylsiloxane (PECOSIL FST-422). ^(h)Perfluorononylethylcarboxydecyl lauryl/behenyl polydimethylsiloxane (PECOSIL FST-41222).^(i)Sulfur-containing organosilane (SI 75). ^(j)Diphenyl guanidine.^(k)2,2′-Dithiobis(benzothiazole).^(l)N-tert-butyl-2-benzothiazole-sulfenamide.

TABLE 4A Stage Time Condition Master Batch Stage (initial 0 min Chargepolymers temp: 90-95° C., rotor rpm 0.5 min Charge oil, filler andstarted at 50 and increased other master batch to 90 at 4.5 min)ingredients 5.5 min Drop based on time or max temperature of 165° C.Remill Stage (initial temp: 0 min Charge master batch 100-105° C., rotorrpm at 0.5 min Charge silica and silane 50) 3.5 min Drop based on timeor max temperature of 150° C. Final Batch Stage (initial 0 sec Chargemaster batch temp: 60-65° C., rotor rpm 30 seconds Charge curatives at40) 150 seconds Drop on mixing time or max temperature of 110° C.

As shown in Table 4, Example 7 was prepared as a control using ahydrocarbon-only conventional paraffin wax against which thesilicone-containing waxes used in Examples 8-15 can be compared.Following the final batch stage, the rubber compositions were sheetedinto specimens of different shapes, which in turn were respectively usedin the different tests described in paragraphs 77-78 below. Thespecimens were then cured at 171° C. for a proper duration as determinedby a cure test for the composition from each Example, thereby formingrespective differently shaped vulcanizate specimens for each of Examples7-15.

The vulcanizate samples for Examples 7-15 were subjected to contactangle tests and wet-skid tests, and the results of those tests areprovided in Table 5 below. The contact angle tests for Examples 7-15were performed in the same manner as described above on the vulcanizatesurfaces of the Examples that were not cleaned prior to testing [i.e.,in the same manner as (B) above for Examples 1-6] using 6 droplets ofdeionized water about 2 μL in size for each Example. The contact anglevalues in Table 5 are listed as the average measurement±the standarddeviation.

The skid resistance of vulcanized rubber sliders formed from thecompositions of Examples 7-15 were tested with a portable Britishpendulum skid tester (available from Munro Stanley London) on a wet(water) Portland concrete surface. The results are shown in Table 5 andare expressed as the British Pendulum Number (BPN). A higher BPNindicates a higher wet skid resistance. The rubber sliders in this testwere not cleaned with organic solvent prior to the wet skid testing.

TABLE 5 Ex. 7 Ex. 8 Ex. 9 Ex. 10 Ex. 11 Ex. 12 Ex. 13 Ex. 14 Ex. 15Contact 112.3 ± 2.3 105.6 ± 1.6 109.2 ± 1.8 105.3 ± 1.5 102.8 ± 2.9114.2 ± 2.9 119.1 ± 6.6 119.0 ± 4.4 118.9 ± 3.5 angle (°) BPN 38 44.145.1 45.1 45.9 45.7 45.9 46 45.4

Table 5 shows that using a silicone-containing wax adjusts the relativehydrophobicity or hydrophilicity of the vulcanizate as compared to thecontrol vulcanizate of Example 7, which uses a hydrocarbon-only wax.Table 5 also shows that the vulcanizates prepared using asilicone-containing wax, i.e., Examples 8-15, each exhibit better wetskid resistance (as measured by BPN) compared to the control vulcanizateof Example 7 prepared using the hydrocarbon-only wax.

Examples 16-20

Carbon-black containing rubber compositions were prepared according tothe formulations provided in Table 6 utilizing either a chlorinatedhydrocarbon wax, a conventional wax or a combination of the chlorinatedhydrocarbon wax and the conventional wax. The compositions were preparedin a manner similar to Examples 1-6, using a Brabender mixer (300 gramcapacity) and a two-stage mixing procedure as disclosed in Table 1A

TABLE 6 Formulation (phr) Ex. 16 Ex. 17 Ex. 18 Ex. 19 Ex. 20 MasterStyrene- 100 100 100 100 100 Batch butadiene^(a) N339 50 50 50 50 50Carbon black Black oil 10 10 10 10 10 Stearic acid 2 2 2 2 2 6PPD^(b)0.95 0.95 0.95 0.95 0.95 Conventional 2 0 2 0 2 wax^(c) Chlorinated 0 22 4 4 wax^(d) Final Zinc oxide 2.5 2.5 2.5 2.5 2.5 Batch DPG^(e) 0.3 0.30.3 0.3 0.3 MBTS^(f) 0.5 0.5 0.5 0.5 0.5 TBBS^(g) 0.5 0.5 0.5 0.5 0.5Sulfur 1.5 1.5 1.5 1.5 1.5 Total 170.25 170.25 172.25 172.25 174.25^(a)DURADENE 706 available from Firestone Polymers of Akron, OH.^(b)Antioxidant 6PPD. ^(c)Microcrystalline wax blend: 20%microcrystalline and 80% paraffin; melting point ~170° F. (availablefrom Crystal, Inc., United States). ^(d)Chlorez 700 chlorinated wax(available from Dover Chemical Corporation, Dover, Ohio). ^(e)Diphenylguanidine ^(f)2,2′-Dithiobis(benzothiazole).^(g)N-tert-butyl-2-benzothiazole-sulfenamide.

Following the final batch stage, the rubber compositions for Examples16-20 were sheeted into specimens of different shapes, which in turnwere respectively used in the different tests described above forExamples 1-6. The specimens were then cured at 171° C. for a properduration as determined by a cure test for the composition from eachExample, thereby forming respective differently shaped vulcanizatespecimens for each of Examples 16-20.

The vulcanizate samples for Examples 16-20 were subjected to contactangle tests and wet-skid tests, and the results of those tests areprovided in Table 7 below. The contact angle tests for Examples 16-20were performed using a Ramé-Hart Model 500 advanced Goniometer, withdeionized water under ambient conditions. When a dry thin film ofChlorez 700 was deposited on the surface of a glass slide in air (byfirst dissolving 3.0 grams of Chlorex 700 in 30 grams of toluene), thewater contact angle on Chlorez 700 was about 86° (average from 6readings with standard deviation of 0.6°), indicating slighthydrophilicity. The water contact angle for the rubber compositions wasobtained on freshly-cut compound surface with a clean blade. The contactangle values in Table 7 are listed as the average measurement, while therow headed “std. deviation” provides their standard deviations.

The skid resistance of vulcanized rubber sliders formed from thecompositions of Examples 16-20 were tested with a portable Britishpendulum skid tester (available from Munro Stanley London) on a wet(water) Portland concrete surface. Two specimens were tested for eachrubber composition. The results are shown in Table 7 and are expressedas the British Pendulum Number (BPN). For one specimen, prior to thetesting, the edge of the rubber slider to be tested was wiped with atissue soaked with isopropanol for removal of surface contaminants. Noedge cleaning was applied to the other specimen. When a slider wasinstalled onto the pendulum skid tester, at least 12 consecutive testswere carried out. The BPN numbers provided in Table 7 represent theaverage BPN from the 9th to the 12th reads. A higher BPN indicates abetter wet skid resistance.

TABLE 7 Property Ex. 16 Ex. 17 Ex. 18 Ex. 19 Ex. 20 BPN (edge wiped)45.4 46.3 45.6 45.6 46 BPN (edge not wiped) 38.4 44.2 39.6 44.2 39.2Contact angle (°) with 110.6 101.4 109.0 103.0 110.7 water Std.deviation 3.8 4.3 3.1 1.2 0.9 Viscosity (ML1 + 4) at 43.9 45.9 42.6 44.641 130° C. Temp. Sweep at 10 Hz peak tan δ (−15° C., 2%) 0.279 0.2850.265 0.278 0.296 Strain Sweep at 50° C. & 15 Hz G′ at 9.9% (MPa) 2.32.39 2.26 2.44 2.32 tan δ at 9.9% 0.195 0.19 0.194 0.193 0.19 Tensile atRT Mod50% (MPa) 1.61 1.63 1.72 1.74 1.70 Mod300% (MPa) 13.70 13.79 14.6615.40 14.12 Tb^(a) (MPa) 21.2 22.2 21.8 21.1 23 Eb^(b) % 435.9 448.4425.4 390.7 460.7 ^(a)Tension at break ^(b)Elongation at break

Examples 21-25

Silica containing rubber compositions were prepared according to theformulations provided in Table 8 utilizing either a chlorinated wax, aconventional wax or a combination of the chlorinated wax and theconventional wax. The compositions were prepared in a manner similar toExamples 16-20 except that a three-stage mixing procedure (employing aremill as a second step in the master batch stage) instead of atwo-stage mixing procedure was used. The three stage mixing procedureemployed is detailed in Table 4A above.

TABLE 8 Formulation (phr) Ex. 21 Ex. 22 Ex. 23 Ex. 24 Ex. 25 MasterStyrene- 100 100 100 100 100 Batch butadiene^(a) Silica^(b) 50 50 50 5050 Black oil 10 10 10 10 10 Stearic acid 2 2 2 2 2 6PPD^(c) 0.95 0.950.95 0.95 0.95 Conventional 2 0 2 0 2 wax^(d) Chlorinated 0 2 2 4 4wax^(e) Remill Silane Si 75^(f) 5 5 5 5 5 Final Zinc oxide 2.5 2.5 2.52.5 2.5 Batch DPG^(g) 1.4 1.4 1.4 1.4 1.4 MBTS^(h) 2 2 2 2 2 TBBS^(i)0.7 0.7 0.7 0.7 0.7 Sulfur 1.5 1.5 1.5 1.5 1.5 Total 178.05 178.05178.05 178.05 178.05 ^(a)DURADENE 706 available from Firestone Polymersof Akron, OH, a solution SBR having a bound styrene content of 23.5%,vinyl bond content in the butadiene portion of 14%, Tg of −62° C.,viscosity of 55). ^(b)Hi-Sil 190G (PPG Industries). ^(c)Antioxidant6PPD. ^(d)Microcrystalline wax blend: 20% microcrystalline and 80%paraffin; melting point ~170° F. (available from Crystal, Inc., UnitedStates). ^(e)Chlorez 700 chlorinated wax (available from Dover ChemicalCorporation, Dover, Ohio). ^(f)Sulfur-containing organosilane (SI 75)^(g)Diphenyl guanidine ^(h)2,2′-Dithiobis(benzothiazole).^(i)N-tert-butyl-2-benzothiazole-sulfenamide.

Following the final batch stage, the rubber compositions for Examples16-20 were sheeted into specimens of different shapes, which in turnwere respectively used in the different tests described in the followingparagraphs. The specimens were then cured at 171° C. for a properduration as determined by a cure test for the composition from eachExample, thereby forming respective differently shaped vulcanizatespecimens for each of Examples 21-25.

The vulcanizate samples for Examples 21-25 were subjected to contactangle tests and wet-skid tests, and the results of those tests areprovided in Table 9 below. The contact angle tests for Examples 21-25were performed using a Ramé-Hart Model 500 advanced Goniometer, withdeionized water under ambient conditions. When a dry thin film ofChlorez 700 was deposited on the surface of a glass slide in air (byfirst dissolving 3.0 grams of Chlorex 700 in 30 grams of toluene), thewater contact angle on Chlorez 700 was about 86° (average from 6readings with standard deviation of 0.6°), indicating slighthydrophilicity. The water contact angle for the rubber compositions wasobtained on freshly-cut compound surface with a clean blade. The contactangle values in Table 9 are listed as the average measurement, while therow headed “std. deviation” provides their standard deviations.

The skid resistance of vulcanized rubber sliders formed from thecompositions of Examples 21-25 were tested with a portable Britishpendulum skid tester (available from Munro Stanley London) on a wet(water) Portland concrete surface. Two specimens were tested for eachrubber composition. The results are shown in Table 9 and are expressedas the British Pendulum Number (BPN). For one specimen, prior to thetesting, the edge of the rubber slider to be tested was wiped with atissue soaked with isopropoal for removal of surface contaminants. Noedge cleaning was applied to the other specimen. When a slider wasinstalled onto the pendulum skid tester, at least 12 consecutive testswere carried out. The BPN numbers provided in Table 9 represent theaverage BPN from the 9th to the 12th reads. A higher BPN indicates ahigher wet skid resistance.

TABLE 9 Property Ex. 21 Ex. 22 Ex. 23 Ex. 24 Ex. 25 BPN (edge wiped) 4750 48.9 52.8 49.6 BPN (edge not wiped) 41.2 50.6 40.4 51.4 41.2 Contactangle (°) 108.9 93.2 105.9 95.5 107.1 with water Std. deviation 2.5 5.02.8 5.8 4.2 Viscosity 50.9 52.7 50 52 47.5 (ML1 + 4) at 130° C. Temp.Sweep at 10 Hz peak tan δ (−15° C., 2%) 0.248 0.234 0.253 0.244 0.264Strain Sweep at 50° C. & 15 Hz G′ at 9.9% (MPa) 2.87 2.94 2.69 3.01 2.8tan δ at 9.9% 0.191 0.198 0.193 0.2 0.195 Tensile at RT Mod50% (MPa)2.173 2.126 2.083 2.178 2.137 Mod300% (MPa) 16.26 15.83 15.04 16.0815.22 Tb^(a) (MPa) 17.7 18.9 16.4 19.9 19 Eb^(b) % 324.4 346.2 320.7355.2 358.7 ^(a)Tension at break ^(b)Elongation at break

Overall for Examples 16-20 and 21-25, it was observed that forsilica-filled compounds, the compounds containing the chlorinated wax inthe absence of conventional wax (i.e., Examples 22 and 24) exhibitedimproved wet skid resistance (i.e., a higher BPN number) as compared tothe compound containing the conventional wax regardless of whether ornot the slider edge was first cleaned with isopropanol. A similaradvantage was not obtained in compounds containing carbon black (i.e.,Examples 16-20) when the slider edge was first cleaned with isopropanol.In addition, the compounds containing the chlorinated wax in the absenceof conventional wax (i.e., Examples 17, 19, 22 and 24) displayed a lowerwater contact angle in comparison to the compounds containingconventional wax. The bulk physical properties of the compounds ofExamples 16-25 as well as the overall compound processability of thecompounds was not particularly affected by the use of the chlorinatedwax; in other words, the chlorinated wax did not cause any adverseeffect on the bulk properties of the compounds.

Examples 26-29 (Effect of Chlorinated Wax on Ozone Degradation)

Carbon-black containing rubber compositions were prepared according tothe formulations provided in Table 10 utilizing either a chlorinated waxor a conventional wax. The compositions were prepared in a mannersimilar to Examples 1-6, using a two-stage mixing procedure as disclosedin Table 1A.

TABLE 10 Ingredient (phr) Ex. 26 Ex. 27 Ex. 28 Ex. 29 Master BatchStyrene butadiene^(a) 100 100 0 0 Styrene butadiene^(b) 0 0 100 100 N339carbon black 50 50 50 50 conventional wax^(c) 2 0 2 0 chlorinatedwax^(d) 0 3.5 0 3.5 Stearic acid 2 2 2 2 Antioxidant^(e) 1 1 1 1 FinalBatch Zinc oxide 2.5 2.5 2.5 2.5 DPG^(f) 0.3 0.3 0.3 0.3 MBTS^(g) 0.50.5 0.5 0.5 TBBS^(h) 0.5 0.5 0.5 0.5 Sulfur 1.5 1.5 1.5 1.5 ^(a)DURADENE706 available from Firestone Polymers of Akron, OH, a solution SBRhaving a bound Styrene content of 23.5%, vinyl bond content in thebutadiene portion of 14%, Tg of −62° C., viscosity of 55. ^(b)DURADENE739 available from Firestone Polymers of Akron, OH, a tin-coupledsolution SBR having a bound styrene content 20.0, vinyl bond content inthe butadiene portion of 60%, Tg of −34° C., viscosity of 92.^(c)Macrocrystalline wax blend: 20% microcrystalline and 80% paraffin;melting point ~170° F. (available from Crystal, Inc., United States).^(d)Chlorez 700 chlorinated wax (available from Dover ChemicalCorporation, Dover, Ohio). ^(e)Antioxidant 6PPD. ^(f)Diphenyl guanidine.^(g)2,2′-Dithiobis(benzothiazole).^(h)N-tert-butyl-2-benzothiazole-sulfenamide.

Following the final batch stage, the rubber compositions for Examples26-29 were sheeted into specimens of different shapes, which in turnwere respectively used in the different tests described above forExamples 1-6. The specimens were then cured at 171° C. for a properduration as determined by a cure test for the composition from eachExample, thereby forming respective differently shaped vulcanizatespecimens for each of Examples 26-29.

For each of the rubber compositions according to Examples 26-29, anapproximately 2 gram sample of each composition was taken and tested forozone degradation according to the following procedure. Each rubbersample was individually soaked in 200 mL of room temperature chloroformfor 12 hours; thereafter, the rubber sample was removed from thechloroform and vacuum dried in a oven at 60° C. for at least 12 hours.After vacuum drying, the sample was again weighed, and thereafter soakedagain in 200 mL of room temperature chloroform for 12 hours. During thesecond chloroform soaking, each sample was subjected to ozone treatmentfor 10 minutes (ozone gas was bubbled through the chloroform). Ozoneconcentration in the air stream was approximately 5%. After the ozonetreatment in the chloroform was completed, samples were removed fromchloroform and dried in a vacuum oven for at least 12 hours at atemperature of 60° C., then removed from the oven and allowed toequilibrate at ambient conditions for 2 hours and weighed. Weight lossresults are reported in Table 11 below.

TABLE 11 Weight Loss Ex. 26 Ex. 27 Ex. 28 Ex. 29 % by weight 8.24 3.3514.30 8.34

Examples 30-35 (Effect of Chlorinated Wax on Ozone Degradation)

Carbon-black containing rubber compositions were prepared according tothe formulations provided in Table 12 utilizing either a chlorinated waxor a conventional wax. The compositions were prepared in a mannersimilar to Examples 1-6, using a two-stage mixing procedure as disclosedin Table 1A. The calculated amount of chlorine in the final compound isshown in Table 13.

Ozone resistance data as gauged by rubber specimens suspended inchloroform and measured by the procedure described above in paragraph[0112] is reported in Table 14, where the ozone resistance is reportedas the percent of weight loss compared to the original compound. Staticozone resistance data and bent loop ozone resistance data are reportedin Tables 15 and 16, respectively. In order to obtain these ozoneresistance data, samples of the compounds were placed in anozone-containing chamber (50 pphm O₃) at 38° C. for the indicated numberof days. A visual inspection of the sample was made after the end of theindicated number of days and a rating was made according to the criterialisted in Tables 15 and 16. For the static ozone test, specimens thatare 2.54 cm wide×15 cm long×0.2 cm thick are stretched uniaxially to12.5% strain and held at that strain for the duration of the test. Forthe bent loop ozone test, the specimen size is 2.54 cm wide×7.5 cmlong×0.2 cm thick. The specimen is folded lengthwise on itself so thetwo ends touch and a loop is formed between them. The ends are clampedin this position for the duration of the test. Ozone resistance was alsomeasured using a dynamic stress relaxation test during which a sample ofeach compound was placed in an ozone-containing chamber (50 pphm O₃) ateither 0° C. or 30° C. for the indicated number of hours. The dynamicstress relaxation specimens have a test area 1.78 mm wide×51 mmlong×1.90 to 2.80 mm thick. The test sequence each hour is to unixallystretch the specimens to 30% strain and hold at that strain for 50minutes. During the remaining 10 minutes of each hour, the specimens areflexed from 0 to 30% strain at a rate of 182 flexes per minute. Thehourly sequence is repeated continuously for the duration of the test. Avisual inspection of the sample was made after the end of the indicatednumber of hours and a rating was made according to the criteria listedin Table 17.

TABLE 12 Ingredient (phr) Ex. 30 Ex. 31 Ex. 32 Ex. 33 Ex. 34 Ex. 35Master Batch Natural rubber^(a) 50 50 50 50 50 50 Butadiene rubber^(b)50 50 50 50 50 50 N660 carbon black 50 50 50 50 50 50 Conventionalwax^(c) 2.5 0 0 0 0 0 C700^(d) 0 4.4 0 0 0 0 Chloroflo 40^(e) 0 0 3.08 00 0 Paroil 150-LV^(f) 0 0 0 3.46 0 0 Paroil 10-NR^(g) 0 0 0 0 3.06 0Paroil 63-NR^(h) 0 0 0 0 0 3.95 Final Batch ZnO 3 3 3 3 3 3 Stearic acid1 1 1 1 1 1 TMQ^(i) 1 1 1 1 1 1 Naphthenic oil 10 10 10 10 10 106PPD^(j) 2.5 2.5 2.5 2.5 2.5 2.5 Sulfur 2 2 2 2 2 2 TBBS^(k) 1 1 1 1 1 1^(a)TSR5 with dirt less than 0.05% ^(b)Diene 600, available fromFirestone Polymers of Lake Charles, LA, 96% cis, 1% vinyl, Tg of −110°C., Mooney viscosity (ML1 + 4 at 212° F.) of 50. ^(c)Microcrystallinewax blend: 20% microcrystalline and 80% paraffin; melting point ~170° F.(available from Crystal, Inc., United States). ^(d)Chlorez 700chlorinated wax (available from Dover Chemical Corporation, Dover, OH)containing 70-71% by weight chlorine. ^(e)Chlorinated long chainparaffin with 20 or more carbons and containing 39-40% by weightchlorine (available from Dover Chemical Corporation, Dover, OH).^(f)Chlorinated long chain paraffin with 20 or more carbons andcontaining 49-51% by weight chlorine (available from Dover ChemicalCorporation, Dover, OH). ^(g)Chlorinated medium chain paraffin with14-17 carbons and containing 40-41% by weight chlorine (available fromDover Chemical Corporation, Dover, OH). ^(h)Chlorinated medium chainparaffin with 14-17 carbons and containing 62-64% by weight chlorine(available from Dover Chemical Corporation, Dover, OH). ^(i)Polymerized1,2-dihydro-2,2,4-trimethylquinoline antioxidant.^(j)N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine antiozonant.^(k)N-tert-butyl-2-benzothiazole-sulfenamide.

TABLE 13 Chlorine content Ex. 30 Ex. 31 Ex. 32 Ex. 33 Ex. 34 Ex. 35Weight % in 0.0 1.8 0.7 1.0 0.7 1.4 final compound Chlorine 0.0 3.121.23 1.73 1.25 2.49 content (phr) in final compound

TABLE 14 Weight loss Ex. 32 Ex. 33 Ex. 34 Ex. 35 Ex. 36 Ex. 37 Ex. 38 %lost (based on 8.60 7.17 7.79 6.20 6.06 4.74 8.03 original compoundweight)

TABLE 15 Days in Ex. Chamber 30 Ex. 31 Ex. 32 Ex. 33 Ex. 34 Ex. 35 1 0Small Small Small Small Small 2 0 Small Small Small Small Small 3 0Medium Medium Medium Medium Medium 4 0 Medium Medium Medium MediumMedium 7 0 Large Large Large Large Large

TABLE 16 Days in Ex. Chamber 30 Ex. 31 Ex. 32 Ex. 33 Ex. 34 Ex. 35 1 0 00 0 0 0 2 0 Fine Fine Fine Fine Fine 3 0 Fine Fine Fine Fine Fine 4 0Fine Fine Fine Fine Fine 7 0 Fine Fine Fine Fine Fine 8 0 Small SmallSmall Small Small 9 0 Small Small Small Small Small 10 0 Small SmallSmall Small Small 11 0 Small Small Small Small Small 14 0 medium mediummedium medium medium

TABLE 17 Temp/Hours in Chamber Ex. 30 Ex. 31 Ex. 32 Ex. 33 Ex. 34 Ex. 35 0° C.  4 hours 0 Fine Fine Fine Fine Fine 24 hours Fine Small LargeLarge Large Large 30° C.  4 hours 0 0 Fine Fine Fine Fine 24 hours FineFine Small Fine Small Fine

Based upon a review of the compositions and data in Tables 1-17, it canbe seen that the hydrophobicity of rubber surfaces can be altered,either increased or decreased, by the use of halogenated waxes. Examplesare the comparisons of Examples 4 and 5 to Examples 1, 2 and 6 in acarbon black reinforced formulation, and the comparisons of Examples12-15 to Examples 7-11 in a silica reinforced formulation, and thecomparisons of Examples 17 and 19 to Example 16 in a carbon blackreinforced formulation, and the comparison of Examples 22 and 24 toExample 21 in a silica reinforced formulation. The adhesion of rubber toa substrate both directly and in the presence of a liquid involves anumber of physical parameters and is difficult to predict (see B. J.Briscoe in “Polymer Surfaces”, D. T. Clark and W. J. Feast, Eds., JohnWiley & Sons, New York, 1978, Chapt. 2.) The friction of rubber whensliding against a substrate, both directly and in the presence of aliquid, involves additional physical parameters and is also difficult topredict (see A. Schallamach and K. Grosch in “Mechanics of PneumaticTires”, S. K. Clark, Ed., U.S. Department of Transportation, Washington,1981, Chapt. 6). Consequently, the usefulness of contact angle changesinduced by the various chlorinated, fluorinated and silicone waxes is intheir application as a compounding tool to enhance tire traction. Asevidenced in the experiment of Examples 16-20 and the experiment ofExamples 21-25, increased skid resistance can be achieved for examplethrough the use of chlorinated waxes and oils as gauged by the BPN.Further usefulness was discovered in the ability of chlorinated waxes toenhance ozone resistance within the bulk rubber. In the experiment ofExamples 26-29 and in the experiment of Examples 30-35, the chlorinecontent of the different waxes differs, and accordingly, the overallchlorine content of the rubber compound differs. The results show thatthe chlorinated waxes increased the ozone resistance of the rubbercompounds, as evidenced by lower weight % losses of all chlorinatedExamples in Table 14 and by all but one chlorinated Example in Table 11.The benefits of the chlorinated waxes are in their propensity to enhanceozone resistance of the interior of the rubber, since static and dynamicozone resistance as measured by surface appearance techniques was notenhanced in the chlorine wax-containing samples (Tables 15 and 16).

Examples 36-44

Carbon-black containing rubber compositions were prepared according tothe formulations provided in Table 18 utilizing either a solidchlorinated wax, a liquid chlorinated wax, or a conventional wax. Thecompositions were prepared in a manner similar to Examples 1-6, using atwo-stage mixing procedure as disclosed in Table 1A. The calculatedamount of chlorine in the final compound is shown in Table 19.

Following the final batch stage, the rubber compositions were sheetedinto specimens of different shapes for each of Examples 36-44, which inturn were respectively used in the different tests with data reportedbelow in Table 20. The specimens were cured at 171° C. for a properduration as determined by a cure test for the composition from eachExample, thereby forming respective differently shaped vulcanizatespecimens for each of Examples 36-44. The vulcanizate specimens forExamples 36-44 were subject to various tests, and the results of thosetests are provided in Table 20 below.

The dynamic viscoelastic properties of the vulcanizate specimens weremeasured by three different tests, as described above for Examples 1-6.The second dynamic viscoelastic test was a dynamic strain sweep testperformed as described above for Examples 1-6. The third viscoelastictest was a dynamic compression test performed as described above forExamples 1-6. Tensile mechanical properties of the vulcanizate sampleswere determined as described above for Examples 1-6.

The skid resistance of vulcanized rubber sliders formed from thecompositions of Examples 36-44 were tested with a portable Britishpendulum skid tester (available from Munro Stanley London) on a wet(water) Portland concrete surface. The results are shown in Table 20 andare expressed as the British Pendulum Number (BPN). A higher BPNindicates a higher wet skid resistance. The rubber sliders in this testwere either cleaned with organic solvent (isopropanol) or not cleanedprior to the wet skid testing, as indicated in Table 20.

TABLE 18 Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ingredient (phr) Ex. 36 37 3839 40 41 42 43 44 Master Styrene butadiene 100 100 Batch #1^(a) Styrenebutadiene 100 100 100 100 100 100 100 #2^(b) N339 carbon black 50 50 5050 50 50 50 50 50 Conventional wax^(c) 2 0 2 0 0 0 0 0 0 Liquidchlorinated 0 0 0 0 2.4 0 0 0 0 wax #1^(d) Paroil 150-LV^(e) 0 0 0 0 02.62 0 0 0 Paroil 10-NR^(f) 0 0 0 0 0 0 2.4 0 0 Paroil 63-NR^(g) 0 0 0 00 0 0 2.62 Chlorinated wax^(h) 0 0 0 0 0 0 0 0 3.5 Stearic acid 2 2 2 22 2 2 2 2 Antioxidant^(i) 1 1 1 1 1 1 1 1 1 Final Zinc oxide 2.5 2.5 2.52.5 2.5 2.5 2.5 2.5 2.5 Batch DPG^(j) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.30.3 MBTS^(k) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 TBBS^(l) 0.5 0.5 0.50.5 0.5 0.5 0.5 0.5 0.5 Sulfur 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5^(a)DURADENE 706 available from Firestone Polymers of Akron, OH, asolution SBR having a bound styrene content of 23.5%, vinyl bond contentin the butadiene portion of 14%, Tg of −62° C., viscosity of 55.^(b)DURADENE 739 available from Firestone Polymers of Akron, OH, atin-coupled solution SBR having a bound styrene content 20.0, vinyl bondcontent in the butadiene portion of 60%, Tg of −34° C., viscosity of 92.^(c)Microcrystalline wax blend: 20% microcrystalline and 80% paraffin;melting point ~170° F. (available from Crystal, Inc., United States).^(d)Chloroflo 40 (available from Dover Chemical Corporation, Dover,Ohio). ^(e)Chlorinated long chain paraffin with 20 or more carbons andcontaining 49-51% by weight chlorine (available from Dover ChemicalCorporation, Dover, OH). ^(f)Chlorinated medium chain paraffin with14-17 carbons and containing 40-41% by weight chlorine (available fromDover Chemical Corporation, Dover, OH). ^(g)Chlorinated medium chainparaffin with 14-17 carbons and containing 62-64% by weight chlorine(available from Dover Chemical Corporation, Dover, OH). ^(h)Chlorez 700chlorinated wax (available from Dover Chemical Corporation, Dover,Ohio). ^(i)Antioxidant 6PPD.

TABLE 19 Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Chlorine content 36 37 3839 40 41 42 43 44 Weight % in final 0 0 0 0 0.58 0.81 0.60 1.04 1.53compound

TABLE 20 Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Property Ex. 36 37 38 39 40 4142 43 44 BPN (edge wiped) 38.6 36.1 45.9 46.0 45.7 45.57 48 48.86 47.86BPN (edge not 36.0 38.6 44.4 46.0 48.9 46.57 48 49 46.71 wiped)Viscosity (ML1 + 4) 43.7 48.2 44.4 49.7 46 46 45.5 46.8 47.9 at 130° C.Temp. Sweep at 10 Hz peak tan δ (−15° C., 0.765 0.807 0.913 0.969 0.9570.923 0.945 0.940 0.945 2%) T at peak tan δ (° C.) −45.9 −45.9 −13.9−13.9 −13.9 −14.0 −13.9 −13.9 −11.9 Strain Sweep at 50° C. & 15 Hz G′ at9.9% (MPa) 3.46 3.11 3.99 4.02 3.77 4 3.75 4.01 4.87 tan δ at 9.9% 0.2620.256 0.682 0.687 0.657 0.679 0.629 0.684 0.723 Tensile at RT Mod50%(MPa) 1.31 1.36 1.59 1.68 1.53 1.58 1.61 1.59 1.78 Mod300% (MPa) 11.8112.38 15.02 16.48 15.56 15.76 15.88 15.95 18.08 Tb^(a) (MPa) 16.2 17.514.8 16 15.2 17.4 16.6 16.7 15.8 Eb^(b) % 385.3 396.3 290.6 291.6 295.8324.3 311.5 312.4 273.7 ^(a)Tension at break ^(b)Elongation at break

Examples 45-53

Silica-filled rubber compositions were prepared according to theformulations provided in Table 21 utilizing either a solid chlorinatedwax, a liquid chlorinated wax, or a conventional wax. The compositionswere prepared in a manner similar to Examples 7-15, using a three-stagemixing procedure as disclosed in Table 4A. The calculated amount ofchlorine in the final compound is shown in Table 22.

Following the final batch stage, the rubber compositions were sheetedinto specimens of different shapes for each of Examples 45-53, which inturn were respectively used in the different tests with data reportedbelow in Table 23. The specimens were cured at 165° C. for a properduration as determined by a cure test for the composition from eachExample, thereby forming respective differently shaped-vulcanizatespecimens for each of Examples 45-53. The vulcanizate specimens forExamples 45-53 were subjected to various tests, and the results of thosetests are provided in Table 23 below.

The dynamic viscoelastic properties of the vulcanizate specimens weremeasured by three different tests, as described above for Examples 1-6.The second dynamic viscoelastic test was a dynamic strain sweep testperformed as described above for Examples 1-6. The third viscoelastictest was a dynamic compression test performed as described above forExamples 1-6. Tensile mechanical properties of the vulcanizate sampleswere determined as described above for Examples 1-6.

The skid resistance of vulcanized rubber sliders formed from thecompositions of Examples 45-53 were tested with a portable Britishpendulum skid tester (available from Munro Stanley London) on a wet(water) Portland concrete surface. The results are shown in Table 23 andare expressed as the British Pendulum Number (BPN). A higher BPNindicates a higher wet skid resistance. The rubber sliders in this testwere either cleaned with organic solvent (isopropanol) or not cleanedprior to the wet skid testing, as indicated in Table 23.

TABLE 21 Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ingredient (phr) Ex. 45 46 4748 49 50 51 52 53 Master Styrene butadiene 100 100 0 0 0 0 0 0 0 Batch#1^(a) Styrene butadiene 0 0 100 100 100 100 100 100 100 #2^(b) silica52.5 52.5 52.5 52.5 52.5 52.5 52.5 52.5 52.5 Black Oil 10 10 10 10 10 1010 10 10 Conventional 2 0 2 0 0 0 0 0 0 wax^(c) Liquid chlorinated 0 0 00 2.4 0 0 0 0 wax #1^(d) Liquid chlorinated 0 0 0 0 0 2.62 0 0 0 wax#2^(e) Liquid chlorinated 0 0 0 0 0 0 2.4 0 0 wax #3^(f) Liquidchlorinated 0 0 0 0 0 0 0 2.62 wax #4^(g) chlorinated wax^(h) 0 0 0 0 00 0 0 3.5 Stearic acid 2 2 2 2 2 2 2 2 2 Antioxidant^(i) 1 1 1 1 1 1 1 11 Remill Silica 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Silane^(j) 5 5 5 5 55 5 5 5 Final Zinc oxide 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 BatchDPG^(k) 1.4 1.4 1.4 1.4 1.4 1.4 1.4 1.4 1.4 MBTS^(l) 2 2 2 2 2 2 2 2 2TBBS^(m) 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 Sulfur 1.5 1.5 1.5 1.5 1.51.5 1.5 1.5 1.5 ^(a)DURADENE 706 available from Firestone Polymers ofAkron, OH, a solution SBR having a bound styrene content of 23.5%, vinylbond content in the butadiene portion of 14%, Tg of −62° C., viscosityof 55. ^(b)DURADENE 739 available from Firestone Polymers of Akron, OH,a tin-coupled solution SBR having a bound styrene content 20.0, vinylbond content in the butadiene portion of 60%, Tg of −34° C., viscosityof 92. ^(c)Microcrystalline wax blend: 20% microcrystalline and 80%paraffin; melting point ~170° F. (available from Crystal, Inc., UnitedStates). ^(d)Chloroflo 40 (available from Dover Chemical Corporation,Dover, Ohio). ^(e)Chlorinated long chain paraffin with 20 or morecarbons and containing 49-51% by weight chlorine (available from DoverChemical Corporation, Dover, OH). ^(f)Chlorinated medium chain paraffinwith 14-17 carbons and containing 40-41% by weight chlorine (availablefrom Dover Chemical Corporation, Dover, OH). ^(g)Chlorinated mediumchain paraffin with 14-17 carbons and containing 62-64% by weightchlorine (available from Dover Chemical Corporation, Dover, OH).^(h)Chlorez 700 chlorinated wax (available from Dover ChemicalCorporation, Dover, Ohio). ^(i)Antioxidant 6PPD. ^(j)Sulfur-containingorganosilane (SI 75). ^(k)Diphenyl guanidine.^(l)2,2′-Dithiobis(benzothiazole).^(m)N-tert-butyl-2-benzothiazole-sulfenamide.

TABLE 22 Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Chlorine content 45 46 4748 49 50 51 52 53 Weight % in final 0 0 0 0 0.51 0.71 0.52 0.91 1.34compound

TABLE 23 Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Property Ex. 45 46 47 48 49 5051 52 53 BPN (edge wiped) 41.3 45.4 48.7 50.3 51.6 50.1 51.1 51.1 50.9BPN (edge not 35.0 41.0 40.0 44.6 50.0 51.9 52.7 52.1 53.7 wiped)Viscosity (ML1 + 4) 44.3 46.8 48.4 52.5 49.7 50 49 49.8 51 at 130° C.Temp. Sweep at 10 Hz peak tan δ (−15° C., −44 −44.0 −12.0 −12.0 −12.0−12.0 −14 −12.0 −10.0 2%) T at peak tan δ (° C.) 0.760 0.798 0.806 0.8290.845 0.848 0.833 0.838 0.821 Strain Sweep at 50° C. & 15 Hz G′ at 9.9%(MPa) 3.81 3.44 5.7 5.52 5.3 5.48 5.09 5.38 5.82 tan δ at 9.9% 0.2840.282 0.787 0.803 0.762 0.794 0.747 0.789 0.822 Tensile at RT Mod50%(MPa) 1.70 1.69 2.06 2.1 2.07 2.03 2.02 2.02 2.17 Mod300% (MPa) 7.797.90 9.92 10.53 10.23 9.95 9.86 9.83 11.11 Tb^(a) (MPa) 14.8 15.6 13.813.7 14.1 14.3 13.6 15.3 13 Eb^(b) % 312.9 316.7 254.8 241.5 252.9 260.8252.4 274.5 223.8 ^(a)Tension at break ^(b)Elongation at break

Analyzing the data provided in Tables 20 and 23, when the rubber slidersurface was not cleaned prior to testing, the compounds containingchlorinated wax (regardless of type of reinforcing filler and type ofchlorinated wax—liquid or solid) exhibit the most prominent enhancementin wet skid resistance as compared to the control compounds containingconventional wax. Comparing the compounds containing solid chlorinatedwax to those containing liquid chlorinated wax shows no obviously higherloss tangent at 50° C., but does show some improvement in wearresistance to the constant-slip Lambourn wear testing.

To the extent that the term “includes” or “including” is used in thespecification or the claims, it is intended to be inclusive in a mannersimilar to the term “comprising” as that term is interpreted whenemployed as a transitional word in a claim. Furthermore, to the extentthat the term “or” is employed (e.g., A or B) it is intended to mean “Aor B or both.” When the applicants intend to indicate “only A or B butnot both” then the term “only A or B but not both” will be employed.Thus, use of the term “or” herein is the inclusive, and not theexclusive use. See Bryan A. Garner, A Dictionary of Modern Legal Usage624 (2d. Ed. 1995). Also, to the extent that the terms “in” or “into”are used in the specification or the claims, it is intended toadditionally mean “on” or “onto.” Furthermore, to the extent the term“connect” is used in the specification or claims, it is intended to meannot only “directly connected to,” but also “indirectly connected to”such as connected through another component or components.

While the present application has been illustrated by the description ofembodiments thereof, and while the embodiments have been described inconsiderable detail, it is not the intention of the applicants torestrict or in any way limit the scope of the appended claims to suchdetail. Additional advantages and modifications will readily appear tothose skilled in the art. Therefore, the application, in its broaderaspects, is not limited to the specific details, the representativeapparatus, and illustrative examples shown and described. Accordingly,departures may be made from such details without departing from thespirit or scope of the applicant's general inventive concept.

As used in the description of the invention and the appended claims, thesingular forms “a,” “an,” and “the” are intended to include the pluralforms as well, unless the context clearly indicates otherwise.

All references incorporated herein by reference are incorporated intheir entirety unless otherwise stated.

What is claimed is:
 1. A tire comprising a tire tread, the tire treadprepared from a rubber composition comprising: (a) at least oneconjugated diene-containing polymer or copolymer comprising at least oneconjugated diene monomer and optionally at least one vinyl-containingmonomer; (b) at least one filler in an amount of 30 to 100 phr whereinat least a majority of the filler is carbon black, silica, or acombination thereof; (c) a curative package; and (d) from 0.2 to 10 phrof at least one halogenated hydrocarbon wax.
 2. The tire of claim 1,wherein the at least one halogenated hydrocarbon wax of (d) comprises atleast one fluorinated hydrocarbon wax in an amount of 0.5 to 5 phr. 3.The tire of claim 1, wherein the at least one halogenated hydrocarbonwax of (d) comprises at least one chlorinated hydrocarbon wax in anamount of 0.5 to 5 phr.
 4. The tire of claim 1, wherein the at least onehalogenated hydrocarbon wax of (d) comprises at least one fluorinatedhydrocarbon wax comprising 0.2% to 70% by weight fluorine based on thetotal weight of the wax.
 5. The tire of claim 1, wherein the at leastone halogenated hydrocarbon wax of (d) comprises a fluorinated paraffinwax.
 6. The tire of claim 1, wherein the at least one halogenatedhydrocarbon wax of (d) is at least one fluorinated hydrocarbon wax thatis solid at temperatures from 20 ° C. to 25° C.
 7. The tire of claim 1,wherein the at least one halogenated hydrocarbon wax of (d) is at leastone chlorinated hydrocarbon wax comprising 35% to 75% by weight chlorinebased on the total weight of the wax.
 8. The tire of claim 1, whereinthe at least one halogenated hydrocarbon wax of (d) comprises achlorinated paraffin wax.
 9. The tire of claim 1, wherein the at leastone halogenated hydrocarbon wax of (d) comprises a chlorinatedhydrocarbon wax that is solid at temperatures from 20° C. to 25° C. 10.The tire of claim 1, wherein the at least one halogenated hydrocarbonwax of (d) comprises a fluorinated hydrocarbon wax that is solid attemperatures from 20° C. to 25° C.
 11. The tire of claim 2, wherein therubber composition further comprises a conventional wax selected fromthe group consisting of a microcrystalline wax, a paraffin wax, andcombinations thereof.
 12. The tire of claim 1, wherein the at least oneconjugated diene polymer or copolymer is derived from a conjugated dienemonomer selected from the group consisting of 1,3-butadiene, isoprene,1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene,2-ethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene,4-methyl-1,3-pentadiene, 2,4-hexadiene, optionally in combination with avinyl aromatic monomer selected from the group consisting of styrene,α-methylstyrene, p-methylstyrene, o-methylstyrene, p-butylstyrene,vinylnaphthalene, and combinations thereof.
 13. The tire of claim 1,wherein the at least one filler further comprises clay, metal oxide, andcombinations thereof.
 14. The tire of claim 1, wherein the at least oneconjugated diene-containing polymer or copolymer comprising at least oneconjugated diene monomer and optionally at least one vinyl-containingmonomer is selected from the group consisting of polybutadiene,styrene-butadiene copolymer, polyisoprene, natural rubber, andcombinations thereof.
 15. The tire of claim 1, wherein a rubber formedfrom the rubber composition exhibits an adjusted surface hydrophobicityor hydrophilicity as measured by a contact angle with water differentfrom that of a rubber formed from a comparative composition, wherein thecomparative composition is the same as the composition of any one ofclaims 1-2, 3 except that the comparative composition contains aconventional wax instead of (d) and the conventional wax is present inthe same amount as (d).
 16. The tire of claim 1, wherein (d) is selectedfrom the group consisting of chlorinated hydrocarbon wax, brominatedhydrocarbon wax, iodated hydrocarbon wax, fluorinated hydrocarbon wax,and combinations thereof.
 17. The tire of claim 1, wherein the 0.2 to 10phr of at least one halogenated wax is selected from the groupconsisting of chlorinated hydrocarbon wax that is solid at temperaturesfrom 20° C. to 25° C., brominated hydrocarbon wax, iodated hydrocarbonwax, fluorinated hydrocarbon wax, and combinations thereof.